Organic Reactions, Volume 73

Published by John Wiley & Sons, Inc., Hoboken. New Jersey Copyright © 2008 by Organic Reactions. Inc. All rights reserved. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act. without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc.. 222 Rosewood Drive. Danvers, MA 01923. (978) 750-8400. fax (978) 750-4470. or on the web at www.copyright.com. Requests for permission need to be made jointly to both the publisher. John Wiley & Sons. Inc.. and the copyright holder. Organic Reactions. Inc. Requests to John Wiley & Sons, Inc.. for permissions should be addressed to the Permissions Department. John Wiley & Sons. Inc.. 111 River Street, Hoboken, NJ 07030. (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley.com/go/permission. Requests to Organic Reactions. Inc.. for permissions should be addressed to Dr. Jeffery Press, 22 Bear Berry Lane, Brewster, NY 10509, E-Mail: [email protected]. Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762-2974. outside the United States at (317) 572-3993 or fax (317) 572-4002. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com. Library of Congress Catalog Card Number: 42-20265 ISBN 978-0-470-43690-5 Printed in the United States of America 109 8 7 6 5 4 3 2 1

CONTENTS

CHAPTER

1.

PAGE

ALLYLBORATION OF CARBONYL COMPOUNDS Hugo Lachance and Dennis G. Hall . . . . . . . . . . . . . . . . . . . . .

1

CUMULATIVE CHAPTER TITLES BY VOLUME . . . . . . . . . . . . . . . . . . . . . . . 575 AUTHOR INDEX, VOLUMES 1–73 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589 CHAPTER AND TOPIC INDEX, VOLUMES 1–73 . . . . . . . . . . . . . . . . . . . . . . 595

ix

CHAPTER 1

ALLYLBORATION OF CARBONYL COMPOUNDS HUGO LACHANCE and DENNIS G. HALL Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada

CONTENTS ACKNOWLEDGMENTS . . . . . . . . . . . . . . . . . . . . . . . . . INTRODUCTION MECHANISM AND STEREOCHEMISTRY . . . . . . . . . Thermal Uncatalyzed Reactions . . . . . . . . . Lewis Acid Catalyzed Reactions . . . . . . . . . Brønsted Acid Catalyzed Reactions . . . . . . . . . . . . . . . . . . . SCOPE AND LIMITATIONS Preparation of Allylic Boron Reagents . . . . . . . . From Hard Allylic Organometallics . . . . . . . . From Alkenylmetal Precursors . . . . . . . . . From Other Organic Fragments . . . . . . . . . From Boron-Containing Fragments . . . . . . . . Stability and Handling of Allylic Boron Reagents . . . . . . Reactivity of Allylic Boron Reagents . . . . . . . . Work-Up Conditions . . . . . . . . . . . Carbonyl Substrate Generality . . . . . . . . . Diastereoselective Additions to Chiral α-Substituted Carbonyl Substrates . . . . . . . . . . . . . Enantioselective Allylations and Crotylations with Chiral Auxiliary Reagents Chiral Boronate Derivatives . . . . . . . . . Chiral Dialkylboranes . . . . . . . . . . Enantioselective Allylations and Crotylations with Chiral α-Substituted Reagents Enantioselective Additions with Chiral Propargyl Reagents . . . . Enantioselective Additions with Chiral Allenyl Reagents . . . . Enantioselective Additions with Chiral 3-Heterosubstituted Reagents . . Preparation of 1,2-Diols . . . . . . . . . . Preparation of 1,4-Diols, Epoxides, and Amino Alcohols . . . . Lewis and Brønsted Acid Catalyzed Enantioselective Additions . . . Double Diastereoselection with Chiral Carbonyl Substrates . . . . Intramolecular Reactions . . . . . . . . . . Reagents for Multiple Additions . . . . . . . . . [email protected] Organic Reactions, Vol. 73, Edited by Scott E. Denmark et al.  2008 Organic Reactions, Inc. Published by John Wiley & Sons, Inc. 1

. . . . . . . . . . . . . . . .

PAGE 3 3 4 4 6 8 8 8 9 12 14 15 17 18 20 20

. . . . . . . . . . . . . .

22 26 26 30 32 37 37 38 38 40 41 43 46 47

2

ORGANIC REACTIONS

Tandem Reactions . . . . . . . . . . . . . Intramolecular Allylboration . . . . . . . . . . Intermolecular Allylboration . . . . . . . . . . . . . . . . APPLICATIONS TO THE SYNTHESIS OF NATURAL PRODUCTS Enantioselective Additions . . . . . . . . . . . Double Diastereoselection . . . . . . . . . . . Tandem Reactions . . . . . . . . . . . . . Transformations of Residual Groups . . . . . . . . . . . . . . . . . . . COMPARISON WITH OTHER METHODS Methods Employing Allylic Tin Reagents . . . . . . . . Methods Employing Allylic Silicon Reagents . . . . . . . Methods Employing Other Metals . . . . . . . . . . . . . . . . . . . . . EXPERIMENTAL CONDITIONS . . . . . . . . . . . EXPERIMENTAL PROCEDURES (+)-B-Allyl bis(Isopinocampheyl)borane [General Procedure for Preparation of the Reagent Free of MgBr(OMe)] . . . . . . . . . . (R)-1,5-Hexadien-3-ol [Typical Procedure for the Simple Allylation of a Representative . . . . . . . Aldehyde with the AllylB(Ipc)2 Reagent] . (2R,3R)-3-Methyl-4-penten-2-ol [Preparation of (−)-(Z)-Crotyl Bis(isopinocampheyl)borane and a Representative Reaction with Acetaldehyde] . . . (2R,3S)-3-Methyl-4-penten-2-ol [Preparation of (−)-(E)-Crotyl Bis(isopinocampheyl)borane and a Representative Reaction with Acetaldehyde] . . . (R,R)-[(E)-2-Butenyl]diisopropyl Tartrate Boronate [Preparation of the (E)-Crotyl Diisopropyl Tartrate Boronate Reagent] . . . . . . . . (R,R)-[(Z)-2-Butenyl]diisopropyl Tartrate Boronate [Preparation of the (Z)-Crotyl Diisopropyl Tartrate Boronate Reagent] . . . . . . . . (1S,2R)-1-Cyclohexyl-2-methyl-3-buten-1-ol [Representative Procedure for Additions of (E)-Crotyl Diisopropyl Tartrate Boronate to Aldehydes] . . . . (1R,2R)-1-Cyclohexyl-2-methyl-3-buten-1-ol [Representative Procedure for Additions of (Z)-Crotyl Diisopropyl Tartrate Boronate to Aldehydes] . . . . (R)-(+)-1-Phenyl-3-buten-1-ol [Preparation of (1R,2R)-N ,N
-Bis(p-Toluenesulfonamide)-1,2-diamino-1,2-diphenylethane Allyldiazaborolidine and a Representative Reaction with Benzaldehyde] . . . . . . . (1R)-2-[1-Chloro-2-(E)-butenyl]pinacol Boronate [Preparation of a Chiral α-Chloro Allylic Boronate] . . . . . . . . . . . . (1S,2S)-(Z)-4-Chloro-2-methyl-1-phenylbut-3-en-1-ol [Representative Addition of Pinacol (1R)-2-[1-Chloro-2-(E)-butenyl]boronate to Aldehydes] . . . (1R,2S,3R,4S)-2,3-O-[(E)-2-Butenylboryl]-2-phenyl-1,7,7-trimethylbornanediol [Preparation of the (E)-Crotyl Camphordiol Boronate Reagent] . . . . (3R,4R)-3-Methyl-1-undecen-5-yn-4-ol [Representative Procedure for Scandium-Catalyzed E-Crotylation of Aldehydes] . . . . . . (1R,2S,3R,4S)-2,3-O-[(Z)-2-Butenylboryl]-2-phenyl-1,7,7-trimethylbornanediol [Preparation of the (Z)-Crotyl Camphordiol Boronate Reagent] . . . . (3S, 4R)-3-Methyl-1-undecen-5-yn-4-ol [Representative Procedure for Scandium-Catalyzed Z-Crotylation of Aldehydes] . . . . . . (3S)-1-Phenylhex-5-en-3-ol [Representative Allylation Catalyzed by a Chiral . . . . . . . . . . . Diol-SnCl4 Complex] (R)-[(2R,6S)-6-Ethoxy-5,6-dihydro-2H -pyran-2-yl]phenylmethanol [Representative Example of a Tandem Catalytic Enantioselective [4+2] Cycloaddition/Allylboration] . . . . . . . . . . . . . TABULAR SURVEY Chart 1. Acronyms for Ligands Used in Tables . . . . . . . Table 1. Addition of Unsubstituted Allyl Reagents . . . . . . . Table 1A. Non-Aromatic Carbonyl Substrates . . . . . . . Table 1B. Aromatic and Heteroaromatic Carbonyl Substrates . . . .

48 48 50 52 52 54 60 62 65 65 66 69 69 70 70 70 71 71 72 73 74 74

75 76 77 77 78 79 80 80 81 82 85 86 86 183

ALLYLBORATION OF CARBONYL COMPOUNDS Table Table Table Table Table Table Table Table

2. 3. 4. 5. 6. 7. 8. 9.

Addition of Z-Crotyl Reagents . . . Addition of E-Crotyl Reagents . . . Addition of α-Substituted Reagents . . Addition of β-Substituted Reagents . . Addition of γ-Substituted Reagents . . Addition of Allenyl and Propargyl Reagents Addition of Cyclic Reagents . . . Intramolecular Additions . . . . . . . . . . . . REFERENCES

. . . . . . . . .

. . . . . . . . .

. . . . . . . . .

3

. . . . . . . . .

. . . . . . . . .

. . . . . . . . .

212 243 288 338 377 489 513 539 555

ACKNOWLEDGMENTS

The authors are grateful to Prof. Scott Rychnovsky, Prof. Robert Bittman, and Dr. Danielle Soenen for their help in copy-editing and proofreading of this chapter. INTRODUCTION

Allylic boron compounds have gained a prominent position as a useful class of synthetic reagents in the past 25 years. Their general structures, 1 and 2, and their utility in carbonyl additions are shown in Eq. 1. The main use of these reagents is in the stereoselective synthesis of homoallylic alcohols 3 by an allyltransfer reaction to carbonyl compounds. In this process, a new carbon–carbon bond is formed, and up to two new stereogenic centers are created. Moreover, the residual allylic unit can be manipulated through a number of different transformations such as oxidative cleavage, olefin metathesis, and many others. Although less prevalent, the propargyl and allenyl reagents typified by 4 and 5 have also been described (Eqs. 2 and 3). Most examples of allylic boron reagents used in carbonyl additions belong to one of two main classes, boranes (structure 1, Y = alkyl) and boronate derivatives (structure 2, Y = OR or NR2 for bis(sulfonamide) derivatives). This chapter focuses on describing and comparing both classes, and when needed, they will be discussed separately. A chart of ligand structures with the acronyms used in this text can be found preceding the Tables. R3

Y

R1

B R2

Y

R

R4

R6

O

+

R6

5

OH R3 R4

R5 R2 R1

1 Y = alkyl 2 Y = O-alkyl(aryl) or N-alkyl(aryl) Y B 4

O

+ Y

(Eq. 1)

3

R

OH H

R

(Eq. 2)

4

ORGANIC REACTIONS Y B

O

+ Y

R

OH H

R

(Eq. 3)

5

Allylic boron reagents react with several classes of carbonyl compounds and their derivatives, including imines. Their most common use, however, is in nucleophilic additions to aldehydes to produce homoallylic secondary alcohols (i.e., the process of Eq. 1 where R5 = H). This reaction process was discovered by Mikhailov and Bubnov in 1964, who observed the formation of a homoallylic alcohol product from the reaction of triallylborane with aldehydes.1 The first example of allylboration using an allylic boronate was disclosed by Gaudemar and coworkers in 1966.2 The true beginnings of this chemistry in terms of practical synthetic applications can be traced back to the late 1970’s, with Hoffmann’s crucial realization of the regio- and diastereospecific nature of the additions of both crotylboronate isomers to aldehydes (see “Mechanism and Stereochemistry”).3 In the following two decades, the work of Hoffmann, Brown, Roush, and Corey was determinant in maturing carbonyl allylboration chemistry into one of the primary methodological tools in stereoselective synthesis. In particular, numerous syntheses of polyacetate and polypropionate natural products feature stereoselective allylborations as key steps (see “Applications to the Synthesis of Natural Products”). The discovery of the Lewis acid catalyzed manifold by Hall and Miyaura recently opened new doors for further development of this important reaction. In addition to the predominant allyl and crotyl reagents, a large number of allylic borane 1 and boronate derivatives 2 (Eq. 1) with various substituents (R1 –R4 ) have been reported. Interested readers can refer to the comprehensive Tabular Survey at the end of this monograph, which covers the literature up to the end of 2005. Several reviews on allylic boron compounds and other allylmetal reagents and their additions to carbonyl compounds and imines have been written prior to this one,4 – 14 and these sources may be consulted if a more in-depth historical perspective is desired. MECHANISM AND STEREOCHEMISTRY

Thermal Uncatalyzed Reactions Mechanistically, allylic boron reagents belong to the Type I class of carbonyl allylation reagents.15 Type I reactions proceed through a rigid, chairlike transition structure which requires a synclinal orientation of reacting π systems. Although catalytic variants for additions of allylic boronates have been reported recently, the reaction between most allylic boron reagents and aldehydes is spontaneous, irreversible, and requires no external activator. The uncatalyzed reactions of these Type I reagents proceed by way of a six-membered, chairlike transition structure that features a dative bond between the boron and the carbonyl oxygen of the aldehyde (Scheme 1).16 – 20 Competitive kinetics in the addition of

ALLYLBORATION OF CARBONYL COMPOUNDS R3

Y

R1

B R2

5

R1, R2 = H, alkyl, OR, NR2, SiR3, Cl R3 = H, alkyl, CO2R, halogen, B(OR)2 R4 = H, alkyl, aryl, OR, halogen

Y

R4

1 Y = alkyl 2 Y = O-alkyl(aryl) or N-alkyl(aryl)

Y B

RE RZ

R5CHO Y

Y B Y

H RE

O RZR

5

Transition Structure

OBY2

OH

work-up R5

R5 RE 6

RZ

H3O+, or N(CH2CH2OH)3, or H2O2/NaOH

RE

RZ

Scheme 1. Overall aldehyde allylboration process.

an allylboronate to benzaldehyde and deuterobenzaldehyde in different solvents revealed a negative secondary deuterium kinetic isotope effect, which rules out a single-electron transfer mechanism.20 Theoretical studies using ab initio MO and DFT methods strongly suggest that the strength of the dative bond between the boron and the aldehyde carbonyl oxygen in the transition structure is the dominant factor in determining the rate of the reaction.19,20 Indeed, whereas the B–O ˚ and very advanced in the transition state, the incipient bond is short (∼1.6 A) C–C bond between the carbonyl carbon and the allylic unit has merely initi˚ (Fig. 1). A weakly bound B–O coordinated complex was detected ated (∼2.4 A) as an early intermediate in the calculated reaction pathway.19 Not surprisingly, allylboration reactions tend to proceed faster in non-coordinating solvents, and the most electrophilic boron reagents react faster.21

Figure 1. Calculated transition structure for the allylboration reaction between B-allyl-1, 3,2-dioxaborolane (CH2 =CHCH2 B[OCH2 ]2 ) and formaldehyde at the MP2/6-31G** level of theory. Indicated bond distances are in angstrom. Reprinted with permission from J. Org. Chem. 1998, 63, 8331.19 Copyright 1998 American Chemical Society.

6

ORGANIC REACTIONS

The immediate products of additions between carbonyl substrates and allylic boranes 1 or boronate derivatives 2 are borinate or borate esters, respectively. To cleave the covalent B–O bond in these intermediates (structure 6, Scheme 1) and to obtain the desired free alcohol, a hydrolytic or oxidative work-up is required. This issue is discussed in detail in the section “Work-Up Conditions”. In the interest of simplifying chemical equations, specific work-up conditions are not included in most of the examples highlighted in this chapter. One of the main reasons for the popularity of allylic boron reagents in stereocontrolled synthesis is that their additions to aldehydes are reliably highly stereoselective and the outcome is predictable. The diastereospecificity of the reaction was first recognized by Hoffmann and Zeiss using both E- and Z-crotylboronates 7 (Eqs. 4 and 5).3,22 For both crotylboranes and crotylboronates, the additions generally proceed with near-perfect reflection of the olefin geometry of the reagent into the configuration of the product. Specifically, the E-crotylboron reagents (Scheme 1, RE = Me, RZ = H) lead to anti-propanoate products and the Z-crotyl reagents (Scheme 1, RE = H, RZ = Me) lead to syn-products. In both instances, of the two possible chairlike transition structures the favored one places the aldehyde substituent (R5 ) in a pseudo-equatorial orientation. This model, which has been reproduced computationally for both crotylborane17 and crotylboronate18 derivatives, accounts for the high diastereospecificity of most allylborations. Even highly functionalized reagents and most intramolecular additions follow the same trend. O B

+

RCHO

O

(Z)-7 >95:5 Z:E

(Eq. 4)

anti (>85%) 93:7 d.r.

+ O

R

–78° to rt

(E)-7 93:7 E:Z

O B

HO

Et2O

RCHO

Et2O –78° to rt

HO R

(Eq. 5)

syn (>85%) >96:4 d.r.

It is well accepted that the high diastereospecificity of aldehyde allylboration reactions is a consequence of the compact cyclic transition structure. Theoretical calculations have shown that the chairlike transition structure shown in Scheme 1 and Fig. 1 is the lowest in energy relative to other possibilities such as the twistboat conformation.16 With boronate reagents, it has also been suggested that a weak hydrogen bond between the axial boronate oxygen and the hydrogen of the polarized formyl unit contributes to the preference for the transition structure with the aldehyde substituent in the pseudo-equatorial position.23 Lewis Acid Catalyzed Reactions As described above, allylic boron reagents are self-activating, Type I reagents where the allylation is effected by coordination of the aldehyde carbonyl oxygen

ALLYLBORATION OF CARBONYL COMPOUNDS

7

to the boron atom within a cyclic six-membered transition structure. Because of this self-activation mechanism, there would appear to be no advantage to using an external promoter such as a Lewis or Brønsted acid. Furthermore, one could expect an added Lewis acid to compete with the boron atom for the basic aldehyde oxygen, potentially leading to a switch from the highly diastereospecific Type I mechanism to a less selective, open-chain Type II mechanism.15 Recent publications, however, show that the additions of allylic boronates can be efficiently and beneficially catalyzed by several Lewis acids.24 – 28 Allylic boranes are not subject to this catalytic effect.29 For additions of allylic boronates, the rate enhancements observed in the presence of these catalysts are quite dramatic.24,29 For example, the addition of 2-ethoxycarbonyl allylboronate 8 to benzaldehyde to give an exo-methylene butyrolactone requires almost two weeks at room temperature, but only 12 hours in the presence of a catalytic amount of Sc(OTf)3 (Eq. 6).24 Note that in this example the resulting homoallylic alcohol intermediate cyclizes in situ with the carboxy ester group to form a lactone product. O EtO2C Et

O B O

+

Sc(OTf)3 (10 mol%) PhCHO

toluene, rt, 12 h 12 d with no catalyst

8

O Et

(Eq. 6)

Ph (93%) >19:1 d.r.

It is noteworthy that the stereospecificity observed in the thermal reaction is fully preserved under this new catalytic manifold. Furthermore, the presence of a 2-alkoxycarbonyl substituent on the allylic boronate is not necessary for the metal-promoted activation to occur (Eq. 7).24,25 According to mechanistic studies, a chairlike bimolecular transition structure similar to the thermal additions can be proposed for these catalyzed allylborations.29 Control experiments have confirmed the inefficiency of Lewis acids with dialkylallylboranes (Eq. 8). Hence, the catalytic effect is thought to derive from an increase in the electrophilicity of the boron atom through binding of the metal ion to one of the boronate oxygens [transition structure (T.S.) 9], as opposed to coordination of the carbonyl oxygen (T.S. 10).29 O B

OH

PhCHO O

CH2Cl2, –78°, 4 h

Ph

>100X acceleration with Sc(OTf)3 (10 mol%)

OH

PhCHO B

CH2Cl2, –78°, 4 h NO acceleration with Sc(OTf)3 (10 mol%)

(Eq. 7) (—)

Ph

(Eq. 8) (—)

8

ORGANIC REACTIONS H R

R2

4

O

H R2

OR 1

B R 3 OR 1

R

4

OR 1

B R 3 OR 1 LA O

LA

10

9

Coordination of the Lewis acid to the boronate oxygens is thought to decrease the overlap between the oxygen lone electron pairs and the vacant p-orbital of the boron atom. Consequently, the boron center is rendered more electron-deficient, and compensates by strengthening the key boron–carbonyl oxygen interaction and concomitantly lowering the activation energy of the reaction. This idea is consistent with theoretical calculations of the non-catalyzed allylboration19 and from an experimental study consisting of a quantitative survey of steric and electronic effects in the reactions of different allylboronates.21 The latter results led to the conclusion that the rate of a given allylboration can “be rationalized in terms of the relative availability of lone pairs of electrons on the oxygen atoms attached to the boron”. Brønsted Acid Catalyzed Reactions In line with the effect of Lewis acids, the huge rate acceleration in the additions of allylic boronates to aldehydes by strong protic acids such as triflic acid was recently reported.30 In the example of Eq. 9, the reaction yield is almost quantitative after 16 hours at 0◦ under conditions where the use of Sc(OTf)3 gives less than 5% of the product. Interestingly, additions with geometrically defined allylic boronates are not always stereospecific. Although definitive mechanistic studies have not yet appeared, it can be presumed that the origin of the acceleration could be similar to that of Lewis acid catalysis, with activation by protonation of a boronate oxygen in the cyclic chairlike transition structure. O EtO2C

O B O

+

PhCHO

CF3SO3H (10 mol%) toluene, 0°, 16 h

O Ph (99%)

(Eq. 9)

(<5%) with Sc(OTf)3

SCOPE AND LIMITATIONS

Preparation of Allylic Boron Reagents Unlike aldehydes and ketones, allylic boron compounds are not ubiquitous, commercial organic substrates. There are several methods for the preparation of allylic boronates, however, and many of these have been developed in the past decade. This topic has been reviewed recently14 so only the most common methods are emphasized in this section. As a result of the lesser stability of allylic boranes, methods to access these reagents are more limited and it is generally easier to prepare allylic boronates with a wide range of functional groups.

ALLYLBORATION OF CARBONYL COMPOUNDS

9

From Hard Allylic Organometallics. The most common preparation of allylic boranes and boronates is the addition of a reactive allylic metal species to a borinic or boric ester, respectively (Eqs. 10 and 11). Preparations from allyllithium,31 – 34 allylmagnesium,32,35 and allylpotassium22,31,36 – 40 reagents are all well known. These methods are popular because the required allylic anions are quite easy to prepare, and because they generally lead to high yields of products. (R1)2BY Y = OR or Cl

R4 R2

R1

R4 R2

B R

R4 R1

+

R5

R5

3

R

1

M

R3 R5 M = Li, K, Mg

B(OR1)3

R1

(Eq. 10)

R2

regio-1 OR1

R4 R2

B

OR1

R4 +

R5 R3

R5

R3

3

R1 B

2

OR1 B OR1 2 R

(Eq. 11)

regio-2

One potential drawback to this approach is that the allylic metal precursor may not be configurationally stable and may be subject to facile metallotropic rearrangement leading to either constitutional or geometrical isomers (Eq. 12).41 – 43 This is in fact a major problem even with 3-substituted allylic boranes, whose geometrical integrity can be compromised according to Eq. 12 even at temperatures well below 0◦ (see section “Stability and Handling”). Because of their potential configurational instability, and also because of their high sensitivity to air, allylic boranes are not isolated from the process depicted in Eq. 10, but rather are used in situ for their addition to carbonyl substrates. In contrast, allylic boronates are much more stable and can be isolated and purified prior to subsequent carbonyl allylation reactions. R1

M R2

R2

M R

1

R2

M

(Eq. 12)

R1

Another potential problem with the preparations from allylic organometallics is that they often involve highly reactive reagents that can lead to incompatibilities with many functional groups. While these impediments constitute no real problem for simple allyl- or crotylboron reagents, they can lead to poor regio- and stereoselectivities in more substituted examples. Significantly, as shown with the diisopropyl tartrate (DIPT) derivatives (E)-11 and (Z)-11 of Eqs. 13 and 14,37 the use of Schlosser’s “superbase” conditions43 to prepare the configurationally stable crotylpotassium anions allows the preparation of both E- and Z-crotylboronates with very high selectivity from the respective (E)- and (Z)-2-butene. Likewise, the bis(isopinocampheyl)crotylboranes [bis(Ipc)crotylboranes] 12 are prepared by anion trapping with the requisite borinic ester [MeOB(Ipc)2 ] at −78◦ (Eqs. 15 and 16).44 Because of the strong Lewis acidity of the resulting dialkylborane, however, the addition of BF3 is required in order to remove the methoxide anion

10

ORGANIC REACTIONS

and form the desired “free” borane. This additional operation is not required with the less acidic crotylboronates. Moreover, crotyldialkylboranes are too sensitive to be isolated and must be treated immediately with carbonyl substrates (see section on “Stability and Handling”). These approaches using crotylpotassium anions remain the methods of choice for preparing boron-based crotylation reagents, which are very useful in the synthesis of polypropionate natural products (see section “Applications to the Synthesis of Natural Products”). CO2Pr-i t-BuOK/n-BuLi THF, –78° to –50°

– K+

O B

1. (i-PrO)3B, –78° 2. 1 N HCl, Et2O 3. (+)-DIPT, MgSO4

CO2Pr-i

O

(E)-11 (>75%)

(Eq. 13) CO2Pr-i 1. (i-PrO)3B, –78°

t-BuOK/n-BuLi THF, –78° to –25°

K+

O B

2. 1 N HCl, Et2O 3. (+)-DIPT, MgSO4

CO2Pr-i

O

(Z)-11 (>75%)

(Eq. 14) MeOB(Ipc)2 K+

K+

B–

(Ipc) OMe

–78°

(Ipc)

(Ipc) BF3•OEt2

B

–78°

(Ipc)

(E)-12 (>75%)

(Eq. 15)

MeOB(Ipc)2 K+

K+

B–

(Ipc) OMe

–78°

(Ipc)

(Ipc)

B

BF3•OEt2

(Ipc)

–78° (Z)-12 (>75%)

(Eq. 16)

B

OMe

MeOB[(+)-Ipc]2

B

OMe

MeOB[(–)-Ipc]2

A number of other functionalized allylic boron reagents can be made using allylmetal intermediates, including E-3-silyl-substituted reagents,32,38 – 40,45 exemplified by the bis(Ipc) derivative 1345 (Eq. 17), and the useful Z-3-alkoxysubstituted reagents,46 – 48 exemplified by 1448 (Eq. 18). The double bond geometry of 14 arises from the chelated alkyllithium intermediate employed in

ALLYLBORATION OF CARBONYL COMPOUNDS

11

its preparation (Eq. 18).33,46 Like most allylic dialkylboranes, reagents 13 and 14 are not isolated and rather are allowed to react in situ with carbonyl substrates (see section “Stability and Handling”). Me Me Si (i-Pr)2N

Me Me Si (i-Pr)2N

n-BuLi, TMEDA Et2O, 0°

1. MeOB(Ipc)2

Li

2. BF3•OEt2

Me Me Si (i-Pr)2N

B(Ipc)2

(Eq. 17)

13 (—) B(Ipc)2

1. MeOB(Ipc)2

n-BuLi

MeO

MeO

THF, –78°

Li

2. BF3•OEt2

(Eq. 18)

MeO 14 (—)

If the presence of sensitive functional groups poses problems of chemoselectivity in the use of hard allylic metal reagents, allylboronate derivatives also can be accessed by a milder transmetalation of allylic tin species with boron halides.49 This approach has been used by Corey in the synthesis of chiral bis(sulfonamido)boron reagents such as the methallyl reagent 15 (Eq. 19) (see section “Chiral Boronate Derivatives”).50 Ph N Br B N Ph Ts Ts

Sn(Bu-n)3

Ts

Ph

N B

(Eq. 19)

Ph

N Ts 15 (—)

CH2Cl2, 0° to rt

Recently, the enantiomerically enriched α-carbamoyloxycrotylboronate 16 has been synthesized using a similar anti-SE ’ reaction with in situ generated 2-chloro1,3-bis(toluenesulfonyl)-1,3,2-diazaborolidine (Eq. 20). Following a ligandexchange with pinacol, the resulting chiral α-substituted boronate 16 is isolated in a good overall yield with minimal erosion of enantiomeric purity.51 Ts N Cl B N

Ts N B

Ts (n-Bu)3Sn

OC(O)N(Pr-i)2

CH2Cl2, 0° (i-Pr)2N(O)CO

88% ee

N Ts

(Eq. 20) O B

1. HCl, H2O 2. pinacol, pTSA, MgSO4, CH2Cl2

O

(i-Pr)2N(O)CO 16 (83%, 2 steps) 85% ee

12

ORGANIC REACTIONS

From Alkenylmetal Precursors. The reaction of an alkenylmetal with a halomethyl boronic ester also leads to allylic boronates (Eq. 21).52 This strategy takes advantage of the configurational stability of vinylic carbanions and circumvents the rearrangements that can plague allylic metal intermediates. For example, an alkenylmagnesium reagent reacts readily with pinacol chloromethylboronate to give the corresponding isoprenylboronate in good yield (Eq. 22).53 R4 R2

XCH(R5)B(OR1)2 M

R

3

B 3

R

M = Li, Mg, Al, K

MgBr

+ Cl

OR1

R4 R2 R

OR1

(Eq. 21)

5

2

O B

O B

THF O

–78° to rt

(Eq. 22)

O

(73%)

Alkenylmetal reagents are generally more configurationally stable than allylic metal species and so alkylations with these anions are usually more stereoselective than with allylic anions. The low reactivity of many alkenylmetal species, however, can sometimes bring about poor yields in the alkylation step. While the reactions of alkenyllithium54 – 56 and alkenylmagnesium53 reagents with halomethylboronates are well established, the high reactivity of these organometallics limits the type of functional groups that may be present. In this regard, less reactive alkenylaluminum57,58 (Eq. 23) and alkenylcopper26,59,60 reagents (Eq. 24) have been used to produce more sensitive, functionalized allylic boronates such as 2-ethoxycarbonyl derivatives of types 17 and 19 from the corresponding alkyne precursors. In the generic example in Eq. 24, the cis-carbocupration of alkynoic esters provides a weakly nucleophilic and configurationally unstable 1-alkoxycarbonylalkenylcopper intermediate 18, and the presence of hexamethylphosphoric triamide (HMPA) as an additive was found to be crucial to avoid erosion of the E/Z stereoselectivity in the alkylation step with the iodomethylboronate electrophile.26,59,60 Under these conditions, a variety of unsymmetrically substituted 3,3-dialkylated allylboronates 19 have been prepared in over 20 : 1 selectivity, and these reagents have been subsequently employed in the stereoselective preparation of quaternary carbon centers by reaction with aldehydes.

CO2Me

DIBAL-H, HMPA THF, 0°

CO2Me Al(Bu-i)2

Cl

O BO rt

MeO2C

O B

O

17 (80%)

(Eq. 23)

ALLYLBORATION OF CARBONYL COMPOUNDS

CO2R1 R2

3

R2

CO2R1

R 2CuLi THF, –78°

[Cu]

I

O BO

R1O2C R2

HMPA, THF, –78° to 0°

R3 18

13

O B

O

R3 19 >20:1 E:Z

(Eq. 24) One limitation of this preparative method is the concurrent formation of an alkenylboronate, which is formed presumably via α-elimination pathways involving the intermediate ate adduct of addition between the organometallic reagent and the α-haloalkylboronate (Eq. 25).52,61 1. Mg, THF 2.

TBDMSO I

Cl

O BO

TBDMSO

O B

Et2O, –100°

O B

+

O

O OTBDMS (69%) 47:53

(Eq. 25)

The use of enantiomerically pure α-chloroalkyl boronic esters as electrophiles, for example the dicyclohexylboronate 20 obtained from Matteson’s asymmetric homologation method,62 provides access to α-alkyl-substituted allylic boronates. For example, reagent 21 is isolated in very high diastereomeric purity by way of a net inversion of configuration (Eq. 26).63,64 Likewise, the Zn(II)-promoted reaction of alkenylmetal fragments with chiral dichloromethylboronate 22 leads to optically pure α-chloroallylboronates such as 23 (Eq. 27).65 This reagent has a small tendency to isomerize so it is combined directly with aldehydes. Addition of all these α-substituted reagents to aldehydes is highly diastereoselective (see Schemes 8 and 9 under “Enantioselective Allylations”).66,67 Furthermore, the chloride substituent can be displaced with a variety of nucleophiles including metal alkoxides and alkylmetal reagents to provide other useful allylation reagents.68 Cy Li

+

Cl

O B

Cy Cy

O

ZnCl2 THF, –78° to 20°

Cy Cl Cl 22

(Eq. 26)

Cy

Cy Cy

O

Cy O

21 (76%) >99.5:0.5 d.r.

20

O B

O B

MgCl THF, –78°

O B– O Cl2CH

Cy

ZnCl2 (1 eq) –78° to 0°, 5 h

O B

Cy O

Cl 23 (—) >99.5:0.5 d.r.

(Eq. 27)

14

ORGANIC REACTIONS

From Other Organic Fragments. Other direct methods to access allylic boron reagents, including chiral ones such as 2-cyclohexenylborane 24, are based on the hydroboration of 1,3-dienes69 (Eq. 28) and allenes70 (Eq. 29). Allylic boronates can also be accessed by the transition-metal-catalyzed diboration71 (Eq. 30) and silaboration72 (Eq. 31) of dienes and allenes. With allenes as substrates, the use of a chiral phosphoramidite ligand leads to high enantioselectivities in the preparation of chiral 2-borylated α-substituted reagents of type 25 (Eq. 32).73 B[(–)-Ipc]2

THF

+

(Ipc)2BH

(Eq. 28)

–25°, 12 h

from (+)-2-pinene 24 (—) >94% ee

TBDMSO

O

Pt(dba)2 (3 mol%), P(Bu-t)3 (6 mol%)

O

toluene, 50°, 2 h

+ H B 1.5 eq

O

O

O

O B

O

Ni(acac)2 (5 mol%), DIBAL-H (10 mol%)

O +

O O (90%) >99:1 Z:E

2 eq

O

(Eq. 31)

B

PhMe2Si

toluene, 80°, 24 h

O

(Eq. 30)

O

(93%) >99:1 Z:E

1.5 eq

PhMe2Si B

O B

toluene, 80°, 16 h

O

(Eq. 29) O

(86%) Pt(PPh3)4 (3 mol%)

+

B B

O B

TBDMSO

Ph Ph O

P NMe2 O Ph Ph (6 mol%), Pd2(dba)3 (2.5 mol%) O

O

R +

O B B

O

O

O

B

O

toluene, rt, 14 h

(Eq. 32) O B

O R 25 (61-75%) 87-92% ee

(pin2B2)

Allylic boronates with a wide variety of functional groups can also be obtained by the treatment of allylic acetates with pinacolatodiboron [(pin)2 B2 ], although side products of oxidative homodimerization can be observed in some instances (Eq. 33).74

Ph

OAc

(pin)2B2, Pd(dba)2 (5 mol%) DMSO, 50°

Ph

O B (73%)

Ph O

+

Ph (13%)

(Eq. 33)

ALLYLBORATION OF CARBONYL COMPOUNDS

15

Very recently, it was shown that allylic trifluoroborates such as 26 can be prepared stereospecifically from allylic alcohols using a palladium complex made from a pincer ligand (Eq. 34).75 A copper-catalyzed, site selective and stereospecific substitution of allylic carbonates with (pin)2 B2 has been optimized to afford several examples of α-substituted allylic boronates.76 When using the E-isomer of an enantiomerically pure secondary allylic carbonate, the resulting chiral α-substituted allylic boronate 27 is obtained with minimal erosion of enantiomeric purity (Eq. 35). The corresponding Z-configured allylic carbonate affords the other enantiomer, and this stereochemical outcome has been explained with a mechanism involving anti attack of the borylcopper reagent in a conformation minimizing allylic 1,3-strain. Allylic halides are also suitable substrates with pinacolborane as the borylating agent under platinum catalysis.77 As shown in a palladium-catalyzed Stille cross-coupling reaction with soft alkenylmetal electrophiles (Eq. 36),78 transition-metal-catalyzed processes can even tolerate unprotected acidic functionalities. Related Negishi-type coupling strategies have also been employed.79,80

1. PhSe n-Pr

OH

+

[B(OH)2]2

Pd SePh Cl (5 mol%), DMSO/MeOH, 50°, 16 h

BF3–K+

n-Pr

2. aq KHF2

26 (94%)

n-Bu

OCO2Me

Cu(OBu-t) (10 mol%), Xantphos (10 mol%) (pin)2B2 (2.2 eq), THF, 0°, 23 h

98% ee

Sn(Bu-n)3 OH

H + Br

O B O

O B

(Eq. 35)

O

Bu-n 27 (95%) 96% ee

Pd2(dba)3•CHCl3 (3 mol%) PPh3 (12 mol%), HMPA, 50°

(Eq. 34)

H

HO

O B O (63%)

(Eq. 36)

From Boron-Containing Fragments. A number of indirect methods to synthesize more highly functionalized allylic boronates are based on the isomerization or derivatization of organoboron substrates. Selected examples include the homologation of alkenylboronates with chloromethyllithium56,81 (Eq. 37),82 and the allylic rearrangement of 3-siloxyalkenylboronates to give chiral α-chloro derivatives such as 28 (Eq. 38).83 A variant of Eq. 37 using lithiated allyl chloride has also been described.84 The Johnson orthoester Claisen rearrangement of a chiral 3-hydroxypropenylboronic ester leads to an epimeric, separable mixture of α-substituted allylic boronates 29 and 30 (Eq. 39).85,86 A related intermolecular method based on the SN 2’ addition of Grignard reagents has been reported (Eq. 40).87 These reagents are not isolated, rather, they

16

ORGANIC REACTIONS

are immediately combined with aldehydes. Other methods of preparation of allylic boronates involving boronic ester fragments include the isomerization of alkenylboronates (Eq. 41),88 cycloadditions of dienylboronates (Eq. 42),89 and olefin cross-metathesis (Eq. 43).90 OMe

O B

MeO

OBn

ClCH2Li O

THF, –78° to rt

MeO

O B

O

OMe

OBn

(77%)

O B

O B

SOCl2 pet. ether, rt

O

TMSO

(Eq. 37)

(Eq. 38)

O

Cl 28 (75%)

Ph OMe Ph Ph O OMe B O Ph

HO

Ph OMe Ph Ph O OMe B O Ph

MeC(OEt)3, cat. EtCO2H 135° O OEt

Ph OMe Ph Ph O OMe B O Ph

Ph OMe Ph Ph O OMe B O Ph

+

CO2Et 29

O B

Cl

CO2Et (71%) 1:1 (separable)

+

i-PrMgCl

30

O B

THF –15°, 15 min

O

O

(Eq. 40)

i-Pr (—) [IrH2(AcOEt)2(PPh2Me)2]PF6 (3 mol%)

TBDMSO

(Eq. 39)

B(OPr-i)2

TBDMSO

B(OPr-i)2

AcOEt, rt, 10 min (94% conv.) 98:2 E:Z

(Eq. 41) O

B

O

O

O +

toluene Y

B

O

80°, 6 h

O Y

O Y = O, NPh

(quant.)

O

(Eq. 42)

ALLYLBORATION OF CARBONYL COMPOUNDS

Ph

+

O B

cat. (3 mol%) O

CH2Cl2, 40°

O B

Ph

PCy3 cat. = Ru Cl Cl Ph PCy3

17

O

(Eq. 43)

(88%) 91:9 E:Z

Stability and Handling of Allylic Boron Reagents Allylic boronates are more stable to atmospheric oxidation and are thus much easier to handle than the corresponding allylic boranes. The stability of the boronate reagents arises from the partial donation of the lone pairs of electrons on the oxygen atoms into the empty p-orbital of boron. This mesomeric effect is responsible for the upfield shift of the boron atom in 11 B NMR compared to that of allylic boranes (compare allylboronate 31 and allylborane 32).21

O B O

B 2

31 11B NMR (200 MHz, CH Cl ) δ 33 ppm 2 2

32 11B NMR (200 MHz, THF) δ 82 pp m

As a consequence of their superior stability, many types of allylic boronates can be isolated and purified. It should be noted that most pinacol allylic boronic esters and other bulky esters are stable to hydrolysis and can be conveniently purified by chromatography on silica gel. A potential pitfall of all allylic boron compounds is their stereochemical integrity, and substituted allylic boranes are known to undergo reversible borotropic rearrangements at temperatures above −45◦ (see Eq. 12, M = BR2 ).22,91,92 For this reason, allylic boranes are normally not handled under atmospheric conditions, and are rather prepared and employed in situ at low temperatures. These borotropic rearrangements are the bane of stereoselective syntheses since they can scramble the double bond geometry of the reagent. Thus, a major advantage in using allylic boronates compared to boranes is that they are much less prone to such rearrangement. For example, whereas B-crotyl-9-borabicyclo[3.3.1]nonane (B-crotyl-9-BBN) (33) exists as an equilibrating mixture of E- and Z-isomers at room temperature,92 the two isomers of pinacol crotylboronate (7) are sufficiently stable to be independently prepared, isolated, and employed at that temperature (Fig. 2).22,54 The allylic borotropic rearrangement has been studied in detail with a few distinct reagents, including the α-methyl allylic reagents of generic structure 34 (Eq. 44). The dialkylboranes are fluxional at room temperature and exist almost exclusively as the thermodynamically favored crotylborane with a more highly substituted double bond.91 – 93

18

ORGANIC REACTIONS

O B O

O B O

B 33

(Z)-7

(E)-7

inseparable E:Z mixture at room temperature

E:Z isomers readily prepared and handled at room temperature

Figure 2. Comparison of the stereochemical stability of crotylboranes vs crotylboronates. R(Y)

R(Y)

B

B

R(Y)

R(Y)

(Eq. 44)

34 R = alkyl Y = OR Y = NMe2

fast at room temperature stable at room temperature stable up to 200°

The speed of the rearrangement depends on the Lewis acidity of the boron atom.94 Electron-donating substituents that reduce the acidity of boron slow down the process. Thus, whereas a monoamino derivative slowly isomerizes at 150◦ ,95 the corresponding diamino derivative is stable up to a temperature of 200◦ .96 The corresponding boronic esters are less stabilized towards the borotropic rearrangement, but they are stable enough to be conveniently handled at room temperature. The presence of Lewis acids, however, can promote or accelerate the rearrangement.49 These allylic borotropic rearrangements obey first-order kinetics and the absence of crossover products in control experiments demonstrates their intramolecular nature.92 In the case of the B-allyl 9-BBN reagent, the coalescence temperature is 10◦ , which corresponds to a rate of exchange of 330 sec−1 (
G= 13.3 kcal/mol).92 Unsurprisingly, bases such as pyridine completely stop the rearrangement.92,94 Activation parameters of several allylic dialkylboranes have been determined by dynamic NMR spectroscopy.91 Reactivity of Allylic Boron Reagents The boron–oxygen mesomeric effect described in the previous section explains the lower reactivity of allylic boronates towards carbonyl compounds compared to that of allylic boranes. The use of Lewis acids, however, allows boronate derivatives, including hindered ones, to react at temperatures comparable to the analogous boranes. As described above (see section “Mechanism and Stereochemistry”), the most reactive allylic boronates are those with the most electrophilic boron centers.19,21 The nucleophilicity of the γ-position of an allylic boron reagent (the position that forms the new C–C bond with the aldehyde) is also important to the reactivity of the reagent. For example, allylic boronates with

ALLYLBORATION OF CARBONYL COMPOUNDS

alkyl B

alkyl

ArO 2S N B N SO 2Ar

CO 2R O B O

CO 2R

faster

O B O

19

O B O slower

reactivity towards carbonyl compounds

Figure 3. Scale of reactivity for selected allylboron derivatives toward carbonyl compounds.

substituents that reduce electron density at this position, such as 2-ethoxycarbonyl groups,58,59 are correspondingly less reactive than similar allylboronates that lack these groups. Between the crotylboronate isomers, the E-isomer reacts noticeably faster than the Z counterpart.22,34 The electronic and steric effects of different allylic borane and boronate derivatives has been studied by qualitative kinetic analysis.21 The resulting scale of reactivity depicted in Fig. 3 emphasizes the importance of both effects in the reactivity of these boron-based reagents. In general, acyclic boronates react faster than cyclic ones. Moreover, the reaction is quite sensitive to electronic effects. For example, N ,N ,N
,N
-tartramide derivatives react at a much slower rate than the corresponding esters. Allylic dihaloboranes have been isolated and characterized.97 The highly electrophilic difluoroallylborane is predicted to be extremely reactive in carbonyl allylation.19 Allylic difluoroboranes are postulated intermediates in the Lewis acid promoted additions of allylic trifluoroborate salts.98,99 These reagents combine stability and reactivity as desirable attributes in a single class of allylic boron reagents. They are prepared by reaction of the corresponding allylic boronic acids with aqueous KHF2 , and they can be purified by recrystallization and stored as air- and water-stable solids for extended periods of time at room temperature. For example, the crotyl trifluoroborates (E)- and (Z)-35 do not interconvert. Allylic trifluoroborate salts are inert to carbonyl compounds until activated by an external Lewis acid, at which point they become efficient allylating agents that produce homoallylic alcohols in high yields. Instead of aldehyde coordination, this new method of activation is thought to involve a mechanism whereby the electrophilic additive (usually BF3 •OEt2 ) strips off a fluoride anion from the trifluoroborate salt. The expected product of this equilibration is a highly electrophilic tricoordinate allylic difluoroborane, which is thought to react with aldehydes through the usual Type I mechanism. Consistent with this hypothesis, the crotyl reagents (E)- and (Z)-35 provide, in over 90% yield, the respective anti and syn addition products expected from a cyclic, chairlike transition structure (Eq. 45). Although the reaction is usually carried out using two equivalents of BF3 •OEt2 at −78◦ , it can also be performed with as low as 5 mol% of the same additive, albeit at room temperature. A phase-transfer procedure has also been developed.100

20

ORGANIC REACTIONS BF3–K+

R1

+

OH

BF3

R3CHO

R3

CH2Cl2

R2

R1 R2

(Eq. 45)

BF3 (0.05 eq), rt, 3-6 h; or BF3 (2.0 eq), –78°, 15 min R3 = Ph (>90%) >98:2 d.r. R3 = Ph (>90%) >98:2 d.r.

(E)-35 R1 = Me, R2 = H (Z)-35 R1 = H, R2 = Me

Work-Up Conditions The addition of allylic boron reagents to carbonyl compounds first leads to homoallylic alcohol derivatives 36 or 37 that contain a covalent B–O bond (Eqs. 46 and 47). These adducts must be cleaved at the end of the reaction to isolate the free alcohol product from the reaction mixture. To cleave the covalent B–O bond in these intermediates, a hydrolytic or oxidative work-up is required. For additions of allylic boranes, an oxidative work-up of the borinic ester intermediate 36 (R1 = alkyl) with basic hydrogen peroxide is preferred. For additions of allylic boronate derivatives, a simpler hydrolysis (acidic or basic) or triethanolamine exchange22 is generally performed as a means to cleave the borate intermediate 37 (Y = O-alkyl). The facility with which the borate ester is hydrolyzed depends primarily on the size of the substituents, but this operation is usually straightforward. For sensitive carbonyl substrates, the choice of allylic derivative, borane or boronate, may thus be dictated by the particular work-up conditions required. R1

R4 R2

B R3

R6CHO R1

R4

R12BO R6

R5

R5 R2 R3

1 R1 = alkyl

work-up

(Eq. 46)

H2 O2 aq NaOH

36 HO R6

R4 R

Y

2

B R3

R6CHO Y

R5

2 Y = O-alkyl(aryl) or N-alkyl(aryl)

R4

Y2BO R6

R5

R2 R3

work-up

H3O+, or OH−, or N(CH2CH2OH)3

R4 R5

R2

R3

(Eq. 47)

37

Carbonyl Substrate Generality Additions of allylic boron reagents have been reported on a very wide range of classes of functionalized aldehydes. Some types of aldehydes, however, are very reactive and may lead to side-reactions. For example, β,γ-unsaturated aldehydes are notoriously difficult substrates but an indirect procedure for their in situ generation leads to clean products of allylboration.101 Although most examples

ALLYLBORATION OF CARBONYL COMPOUNDS

21

of additions of allylic boron reagents involve aldehydes as substrates, additions to ketones are also possible. Additions to simple ketones are much slower than similar reactions with aldehydes, and forcing conditions may be required. The stereoselectivity observed in these additions is variable depending on the difference in size between the two substituents on the ketone. As exemplified in Eq. 48, ketones react slowly with allylic boronates, under high pressure, to yield tertiary homoallylic alcohols as products.102 Additions of allylic boranes are also much slower with ketones. For example, additions of methallyl-BBN are performed at room temperature, compared to −78◦ for aldehydes (Eq. 49), and they were found to be highly sensitive to the steric bulk of the ketone.103 Because of the high temperature required, these additions are accompanied by reversible allylic rearrangement in reactions of 3-monosubstituted allylic boranes, which renders them impractical. O B

O

+ O

R

pet. ether

HO

8 kbar, 3 d

R

HO +

R

(Eq. 48)

syn

anti

R = Et (79%) 1:1 anti:syn, ~1:2 E:Z R = i-Pr (—) >99:1 anti:syn, ~1:3 E:Z pentane

O

+

HO

(Eq. 49)

rt, 2 h

B

(95%)

The additions of allylic boronates to ketones are greatly enhanced if an appropriate chelating group is present on the ketone (such as an α- or β-hydroxy or carboxylic acid group).104 – 109 For example, both (E)- and (Z)-diisopropyl crotylboronate exchange 2-propanol and add to α-hydroxyacetone within reasonable time frames to give the expected products in high diastereoselectivity (Eq. 50).109 In the proposed transition structure 38, the ketone residue bearing the α-hydroxy group occupies an axial position due to the formation of a cyclic boronate complex. O

O B(OPr- i)2

RE RZ

OH Et 3N, CH 2Cl 2, –78° to rt, 36 h

B OR RE

O RZ 38

OH HO RE RZ

R E = Me, R Z = H (72%) 97:3 d.r. R E = H, R Z = Me (65%) 94:6 d.r.

(Eq. 50) Moderate levels of diastereomeric differentiation are observed in the additions of achiral allylboronates to β-hydroxy ketones, as exemplified in Eq. 51a.110 The major product is tentatively assigned as the anti diastereomer. Few reports describe the use of carbonyl substrates other than aldehydes and ketones, and these reactions have not led to applications. For instance, low reactivity leading

22

ORGANIC REACTIONS

to modest yields and stereoselectivity are observed in the additions of allylic boranes to acylsilanes (Eq. 51b).111 OH O Ph

B(OH)2 CH2Cl2, rt

Et

HO Et OH

HO HO Et

+

Ph

Ph syn

anti

(Eq. 51a)

(84%) 9:1 anti:syn O

B(Ipc)2

+ SiPh3

Et2O

HO SiPh3

(Eq. 51b)

–78° to rt (61%)

Acid chlorides (which react vigorously), esters, and N ,N -dimethylamides react with two equivalents of the reagent to give diallyl tertiary alcohols after work-up (Eq. 52).103

B 2 eq

pentane

O

+ Ph

Cl

HO Ph

(Eq. 52)

rt, 2 h (89%)

The Lewis acid catalyzed reactions expand the scope of aldehyde substrates with certain boronate reagents. For example, whereas cyclohexanecarboxaldehyde is unreactive under thermal (uncatalyzed) conditions, it does react with allylic boronate 8 under Sc(OTf)3 catalysis at room temperature (Eq. 53, see also Eq. 6).26 EtO2C Et

O B O 8

CHO +

O Sc(OTf)3 (10 mol%) toluene, rt, 24 h no reaction with no catalyst at 80°

O Et

(Eq. 53) Cy (54%)

Diastereoselective Additions to Chiral α-Substituted Carbonyl Substrates The presence of a stereogenic center on the aldehyde can strongly influence the diastereoselectivity in allylboration reactions, especially if this center is in the α-position. Predictive rules for nucleophilic addition on such α-substituted carbonyl substrates such as the Felkin model are not always suitable for closed transition structures.112 For α-substituted aldehydes devoid of a polar substituent, Roush has established that the minimization of “gauche-gauche” (“syn-pentane”) interactions can overrule the influence of stereoelectronic effects.113 This model is valid for any 3-monosubstituted allylic boron reagent. For example, although crotylboronate (E)-7 adds to aldehyde 39 to afford as the major product the diastereomer predicted by the Felkin model (Scheme 2),114,115 it is proposed that the dominant factor is rather the minimization of syn-pentane interactions between the γ-substituents of the allyl unit and the α-carbon of the aldehyde. With this

ALLYLBORATION OF CARBONYL COMPOUNDS

O B O

H H

Et

OH Et

O

H

H 39

Felkin product 40

O Et

23

+

O B

83 17

O

(E)-7 O O B

OH Et

O

H H Et

anti-Felkin product

41

Scheme 2. Stereoinduction model for additions of (E)-7 to α-chiral aldehyde 39.

model, 40 is the favored transition structure leading to the Felkin product because the two smallest substituents on the α-carbon (H, Me) are aligned respectively with a methyl and a hydrogen of the E-crotyl unit. This arrangement leaves the largest group (Et) of the aldehyde “outside” the chair, away from the reactive centers and almost orthogonal with the plane of the carbonyl unit. This conformer, which in this instance also happens to be the reactive one predicted by the Felkin model, best minimizes the so-called gauche-gauche (syn-pentane) interactions. In the alternative transition structure 41 that leads to the minor diastereomer, the ethyl group induces slightly more important gauche-gauche interactions compared to those found in 40 (Et–H for 41 vs. Me–H for 40). Other transition structures with the smallest group (H) outside the chair are less favorable and are not considered in this analysis. These transition structures feature Me–Me or Et–Me “syn-pentane” interactions, and thus are significantly higher in energy. The value of this model is more apparent in rationalizing the results of crotylboronate (Z)-7 for which the possible transition structures, 42–45, are shown in Scheme 3.113 In these examples, the major diastereomer is the anti-Felkin product.115 The Felkin transition structure 45 shows a severe Me–Me syn-pentane interaction. Structure 43, analogous to 40 in Scheme 2, best minimizes these interactions by aligning the smallest groups together. With respect to the minor diastereomer, structure 44 is preferable over 45, but not quite as effective as 43 in minimizing the overall effect of syn-pentane interactions because it places the methyl group outside the chair instead of the larger ethyl group. The stereoinductive effect of the α-substituent is often more powerful when this substituent is a polar group such as an alkoxy or amino group. In this instance as well, minimization of syn-pentane interactions with 3-monosubstituted reagents is important, and the selectivity can be amplified if it acts in concert with other effects. Known models include the stereoelectronic preference

24

ORGANIC REACTIONS

O O B

H H

O Et 42

O O B

OH O

O Et

H 39

+

O B

H

Et

Et H

43

anti-Felkin product 70 30

O

(Z)-7

O B O

H H Et

O

OH Et Felkin product

H 44

O B O

H H H

Et

O

45

Scheme 3. Stereoinduction model for additions of (Z)-7 to α-chiral aldehyde 39.

for the orthogonal polar group dictated by the Felkin–Anh model,116 and the minimization of dipoles (i.e., the Cornforth model117 ). With such aldehydes as glyceraldehyde acetals (e.g., 51 in Scheme 4), Z-crotylboron reagents tend to be more selective than the E-isomers.118 In the absence of any γ-substituents, or with 3,3-disubstituted reagents, syn-pentane interactions are not expected to play a key role. As shown in Scheme 4, the generic addition of pinacol allylboronate (31) to aldehydes substituted with a polar substituent can proceed through four reasonable transition structures 46–49 (high-energy rotamers with the small group, the hydrogen atom, in the “outside” position are not considered).115,118 Comparison of the selectivity among aldehydes 39, 50, and 51 shows an increase in the anti product with a polar aldehyde substituent. By presenting the polar group almost

ALLYLBORATION OF CARBONYL COMPOUNDS

25

O O B O

R

X H

46

O O B

OH R O

O R

H X

+

O 31

R H

syn:anti

anti (Felkin–Anh)

O B O O

49 O

O

O Et

X

48

X R

OH R

O

H H

syn (anti-Felkin–Anh)

O B O

H X

X

X

47

O B

H

R

H

H epi-39

OBz 50

62:38

45:55

H

O O 51 20:80

Scheme 4. Stereoinduction model for additions of allylboronate 31 to aldehydes with a polar α-substituent.

perpendicular to the plane of the aldehyde carbonyl group, structures 46 and 49 are stereoelectronically favorable and probably comparable in energy even if structure 49 is formally the reactive conformer according to the Felkin–Anh interpretation. The results of reactions of allylboronate 31 and the corresponding crotyl reagents suggest that with aldehyde 51, the Cornforth-like conformer 48 (minimizing dipole repulsion between the α-alkoxy substituent and the carbonyl)

26

ORGANIC REACTIONS

is particularly important in explaining the increase of the anti stereoisomer. A computational study supports the importance of the Cornforth model in these allylboration reactions.119 Moreover, this conformer (48) also favorably places the large methylene(oxy) substituent of aldehyde 51 on the “outside” on the chairlike transition structure. To improve the levels of selectivity in additions to chiral aldehydes, it is possible to resort to the tactic of double diastereoselection with the use of chiral allylic boranes and boronates (see section “Double Diastereoselection”). Bis(isopinocampheyl) allylic boranes and the tartrate allylic boronates (see following section), in particular, are very useful in the synthesis of polypropionate natural products by reaction with α-methyl and α-alkoxy functionalized aldehydes. Enantioselective Allylations and Crotylations with Chiral Auxiliary Reagents The most common application of the allylboration reaction is in the allylation and crotylation of aldehydes. Many strategies have been devised for controlling the absolute stereoselectivity.10,11 These strategies involve two general classes of chiral reagents: (1) allylic boronates or boranes containing a stereogenic α-carbon on the allylic unit; (2) allylic boronates fitted with a chiral auxiliary that creates the cyclic boronate, or that is attached to the non-allylic substituents in boranes. The use of chiral auxiliary-based reagents is more popular because it is generally easier to manipulate the non-allylic substituents than it is to make an enantiomerically pure allylic boronate with a stereogenic α-carbon on the allylic unit. Several examples of both classes of reagents have been reported and reviewed recently, both for boronate derivatives and boranes.10,11 Chiral Boronate Derivatives. A large number of chiral auxiliary reagents based on allylic boronates has been reported.10,11 This section provides a brief overview of the historically important ones, but it focuses mainly on the most popular systems and the emerging ones (Fig. 4). The first examples of chiral allylic boronates120 were prepared from rigid camphor-derived 1,2-diols, providing allylation reagents of generic structure 52.114,120 – 122 Although they did not provide very high levels of stereoinduction in their reactions with aldehydes, these reagents inspired more work by several other groups, and these efforts led to significantly improved systems. For example, the class of tartrate-derived allenyl-, allyl- 53, and crotylboronates 11 has evolved into one of the most recognizable class of reagents in organic synthesis.37,123,124 These reagents are very reactive, allowing additions to aldehydes to proceed readily at −78◦ . Their reactivity comes at a price, however, as they are hydrolytically unstable and must be employed in conjunction with molecular sieves to rigorously eliminate adventitious traces of water.125 Nonetheless, when appropriately stored at −20◦ , the crotylboronates 11 can be kept for months without appreciable deterioration. As expected, reagents (E)-11 and (Z)-11 give the respective anti- and syn-propionate units in a diastereospecific manner and with very high diastereoselectivity (Eqs. 54 and 55).37 The enantioselectivity tends to be higher

ALLYLBORATION OF CARBONYL COMPOUNDS R1

Ph R3

CO2Pr-i

O

R1

B

27

R

O H

O B

1

O

O

CO2Pr-i

R2

R2

R3

53 R1, R2 = H (E)-11 R1= Me, R2 = H (Z)-11 R1 = H, R2 = Me

52

R1

56

R2 57 (E)-58 (Z)-58 15

R1

O

54 R1 = CH2Ph 55 R1 = CH2CF3

N Ph B N Ts

N SO2Me

N O

Ph

Ts R3

O B

O B

R2

N

R1, R2, R3 = H R1= Me, R2, R3 = H R1 = H, R2 = Me, R3 = H R1, R2 = H, R3 = Me

Figure 4. Common allylic boronate derivatives used as chiral auxiliary reagents in enantioselective carbonyl additions. (Only one stereoisomer is shown for simplicity.)

with (E)-11, but values are typically less than 85% ee for most aldehydes. In this regard, toluene is the best solvent for aliphatic aldehydes whereas THF is optimal for aromatic ones.125 Although simple stereoselection with these reagents does not provide practical levels of enantioselectivity, their use in double diastereoselection with α-substituted aldehydes126 has been amply demonstrated in the context of numerous total syntheses of complex natural products.11 CO2Pr-i O B

+ RCHO

O (R,R)-(E)-11

CO2Pr-i

4 Å MS, –78°

O

(R,R)-(Z)-11

CO2Pr-i

R

(Eq. 54)

anti (70-95%) >98% d.r., up to 88% ee

CO2Pr-i O B

HO

toluene or THF

+

RCHO

toluene or THF 4 Å MS, –78°

HO R

(Eq. 55)

syn (70-95%) >98% d.r., up to 86% ee

Originally, it was proposed that lone pair repulsions between one of the tartrate ester carbonyl oxygens and the aldehyde oxygen in transition structure 60 were responsible for the preference for transition structure 59 and the consequent enantiofacial selectivity (Scheme 5). Recent theoretical calculations,

28

ORGANIC REACTIONS OPr-i O O B O

H

O B

+ RCHO

O (R,R)-53

R

O

R CO2Pr-i

OH

CO2Pr-i

59 favored diastereomeric T.S.

R = Cy (97%) 87% ee R = t-Bu (56%) 86% ee

CO2Pr-i i-PrO2C i-PrO O

OH

O O B

R O R

60

Scheme 5. Model for absolute stereoinduction in additions of tartrate allylic boronate 53 to aldehydes.

however, point to an attractive nO -π*C=O interaction between the basic oxygen atom of one of the two ester groups and the boron-activated aldehyde carbonyl as the main factor favoring transition structure 59 in these stereoselective allylations.127 Significantly higher levels of enantioselectivity can be obtained with aromatic and unsaturated aldehydes by making use of the corresponding metal carbonyl complexes (Eq. 56).128,129 The selectivity is higher in toluene as solvent, and the resulting product can be easily decomplexed oxidatively to afford enantioenriched material. Likewise, dicobalt hexacarbonyl complexes of propargylic aldehydes provide much improved selectivities.128,130 CHO

CO2Pr-i O B

O

(R,R)-53

CO2Pr-i

OH

1. 4 Å MS, toluene, –78°

+ Cr(CO)3

2. CH3CN, O2, hν

Ph (>90%) 83% ee 56% ee with PhCHO

(Eq. 56) Cyclic derivatives 54 and 55 lead to higher levels of enantioselectivity with several types of aldehydes but their preparation requires more effort than the simpler parent reagents 53 and 11 (Fig. 4).131,132 The mixed O/N boronate derivative 56 provides high enantioselectivities with aliphatic aldehydes (Eq. 57).133 Its preparation, however, is also tedious and requires five steps from enantiomerically pure camphorquinone.

ALLYLBORATION OF CARBONYL COMPOUNDS

O B 56

+

OH

Et2O

RCHO

–78°, 2 h

N SO2Me

29

(Eq. 57)

R (47-92%) up to 96% ee

The bis(sulfonamide)-derived reagents (e.g., 57, 58, and 15 in Fig. 4) are based on a 1,2-diamino-1,2-diphenylethane auxiliary.50 These hydrolytically unstable boronate derivatives are typically prepared by Sn-to-B exchange of allylic tin precursors (e.g., Eq. 19). When employed at −78◦ in toluene or methylene chloride, unsubstituted allyl and methallyl reagents 57 and 15 provide very high enantioselectivities (>95% ee).50 The 2-bromoallyl reagent is also quite efficient but the crotylation reagents 58 provide slightly lower enantioselectivities (90–95% ee). It is thought that in the favored transition state 61 involving a tetracoordinate boron atom, the tolylsulfonyl groups orient away from the phenyl substituents of the chiral auxiliary (Scheme 6). It was proposed that the high enantioselectivity can be rationalized by the presence of a steric interaction between the methylene group of the allyl unit and the sulfonyl substituent on the pseudo-equatorial nitrogen atom in the disfavored transition state 62.50 Several 2-substituted derivatives of these bis(sulfonamide) allylation reagents have been employed in the total synthesis of complex natural products (see section “Applications to the Synthesis of Natural Products”). There are only a few examples where chiral allylic boronates react successfully with ketones, and the enantioselectivities are modest.134 A recent report, however,

Tol Ph

O2S

N B N

H O

R

TolO2S N B

Ph Ph N SO2Tol

+ RCHO

OH

Ph R SO2

Tol 61 favored diastereomeric T.S.

R = Ph (>90%) 95% ee R = Cy (>90%) 97% ee

Tol

(S,S)-57

O2S H R

Ph

N O B N

OH

Ph R SO2 Tol

62

Scheme 6. Model for absolute stereoinduction in additions of bis(sulfonamide) reagent 57 to aldehydes.

30

ORGANIC REACTIONS

describes the use of very reactive binaphthol-derived allylboronates. In particular, high levels of enantioselection (>96% ee) are obtained in the reaction of the 3,3
(CF3 )2 -BINOL reagent 63 with several aromatic ketones, as exemplified with 4-chloroacetophenone (Eq. 58).135 O CF3

HO Cl O B O

(Eq. 58)

toluene, –78° to –40°, 48 h

Cl (94%) >99:1 e.r.

CF3

63

Chiral Dialkylboranes. Several allylic boranes have been developed as chiral auxiliary reagents (Fig. 5). The introduction of terpene-based reagents such as 12 and 64–68 has been pioneered by H.C. Brown, and the most popular class remains the bis(isopinocampheyl) derivatives (structures 12, 64–66).136 A wide variety of substituted analogs have been reported,9,12 including the popular crotylboranes 12,44,137 but also a number of other reagents bearing heteroatomsubstituents. All are made from the inexpensive precursor α-pinene, readily available in both enantiomeric forms.

R3 R1

B R

64 (E)-12 (Z)-12 65 66

R3

R3

R1

R1

2

R

R2

R1, R2, R3 = H R1= Me, R2, R3 = H R1 = H, R2 = Me, R3 = H R1, R2 = H, R3 = Me R1, R2 = Me, R3 = H

R

68

TMS B

R2 69

2

67

R3 1

B

B

R1

B R2

70 R1, R2, R3 = H (E)-71 R1= Me, R2, R3 = H (Z)-71 R1 = H, R2 = Me, R3 = H

Figure 5. Chiral allylic boranes used as chiral auxiliary reagents in enantioselective additions to carbonyl compounds. (Only one isomer is shown for simplicity. For reagents 12 and 64–66, (−)-Ipc is shown.).

ALLYLBORATION OF CARBONYL COMPOUNDS

31

Most of the bis(isopinocampheyl) reagents, which are prepared from hard allylic organometallic precursors (e.g., Eqs. 15 and 16), are very reactive and add rapidly to aldehydes at −78◦ . Like other boranes, they are oxidatively unstable in ambient atmosphere and must be reacted with aldehydes in situ. Moreover, because of the borotropic rearrangement discussed above, the crotylboranes must be preserved and used at a low temperature to avoid geometrical isomerization with consequent formation of mixtures of diastereomeric products (see section on “Stability and Handling”). Not surprisingly, the 3,3-disubstituted reagent 66, which provides quaternary carbon centers in the products, reacts more slowly and necessitates a higher reaction temperature.138 The alcohol products from these additions are most often isolated through a basic hydrolytic oxidative work-up of the borinate intermediate (see Eq. 46). The unsubstituted reagent 64, allyl(Ipc)2 borane, is very enantioselective.136 It provides enantioselectivies over 95% for a wide range of aldehyde substrates. The removal of residual Mg2+ salts from the preparation of 64 leads to a dramatic increase of the reagent’s reactivity, allowing reactions to be carried out at −100◦ with improved enantioselectivities (up to 98% ee).139 Simple allylation reactions have been performed successfully in good to high yields with a wide variety of aliphatic, aromatic and heteroaromatic aldehydes (see section “Applications to the Synthesis of Natural Products”). Crotylations of aldehydes with reagents 12 are less selective, providing enantioselectivities in the range of 88–92% ee at −78◦ .137 The bis(isopinocampheyl)boranes behave poorly with ketones as substrates. For example, the simple allylation of acetophenone with reagent 64 gives the addition product with only 5% ee.140 The enantioselectivity of these reagents is explained by comparison of transition structures 72 and 73 shown in Scheme 7. The disfavored transition structure 73 leading to the minor enantiomer displays a steric interaction between the methylene of the allylic unit and the methyl group of one of the pinane units. Unlike the tartrate boronates described above, the directing effect of the bis(isopinocampheyl) allylic boranes is extremely powerful, giving rise to high reagent control in double diastereoselective additions (see section on “Double Diastereoselection”). Other chiral dialkylallylboranes have been reported, including the borolanes 69 (Fig. 5).141,142 Although the high reactivity and outstanding enantioselectivity of these borolanes make them very attractive reagents, they are notorious for their tedious preparation and have thus remained rather under-utilized. Recently, the 10-TMS-9-borabicyclo[3.3.2]decane allylborane and crotylboranes (70) and (71) were shown to provide remarkable stereoselectivities (>98% d.r., 94–99% ee) and good to high yields for a wide range of aldehydes.143 These reagents require reaction times of just a few hours at −78◦ , and are said to be robust and recyclable. They can be prepared using allylic carbanions in three simple steps that includes, however, a resolution of the borinic ester precursor as a stable and crystalline pseudoephedrine complex. The corresponding allenylborane has been reported.144 Reagent 74, the 10-phenyl analog of reagent 70, is particularly effective in allylations of ketones.145 As exemplified in the reaction between (R)-74 and acetophenone, enantioselectivities are excellent for aromatic ketones

32

ORGANIC REACTIONS

HO

R4 H R2

B

R4 B

72 favored diastereomeric T.S.

O

+ R

1

2 R3 R

up to 98% ee with 64

R3 R2

R1

O

R1

R4

H

>98% d.r., 88-92% ee with 12

R3 64 (E)-12 (Z)-12 65 66

R2, R3, R4 = H R2 = Me, R3, R4 = H R2 = H, R3 = Me, R4 = H R2, R3 = H, R4 = Me R2, R3 = Me, R4 = H

H R1 R2

HO R4 O B

R4

R1 R 3 R2

R3 73

Scheme 7. Model for absolute stereoinduction in additions of (−)-bis(isopinocampheyl) allylic boranes to aldehydes.

(Eq. 59), and even surprisingly high for aliphatic ketones such as 2-butanone, a substrate that offers very little steric discrimination (Eq. 60). Reagent 74 is less effective than 70 in allylations of aldehydes (e.g., 90% ee vs. >98% ee for 70 in the allylation of benzaldehyde). The superior reactivity and selectivity of 74 with ketones is ascribed in part to the lesser steric bulk of the phenyl substituent compared to the trimethylsilyl unit of reagent 70. The smaller phenyl substituent of 74 would provide a better fit for ketones in the chiral “pocket” of the reagent. O Ph Et2O, –78°

OH

(Eq. 59)

Ph (92%) 96% ee

Ph B O (R)-74

Et Et2O, –78°

OH

(Eq. 60)

Et (80%) 87% ee

Enantioselective Allylations and Crotylations with Chiral α-Substituted Reagents One major advantage of chiral auxiliary reagents over chiral α-substituted reagents is the fact that the chiral diol or diamine unit is not modified in the bond-making process and is thus potentially recyclable. The preparation of enantiomerically pure α-substituted reagents requires a stereoinductive transformation

ALLYLBORATION OF CARBONYL COMPOUNDS

33

such as the Matteson asymmetric homologation (see Eqs. 26 and 27), and their addition to aldehydes leads to destruction of the stereogenic α-center. Despite these disadvantages, many such reagents have found extensive use in the total synthesis of complex natural products.11 Examples of chiral α-substituted allylic boronates are shown in Fig. 6.4,5 The possibility for allylic rearrangement precludes the use of chiral α-substituted allylic boranes except in special instances such as the cyclohexenyl derivative 24, which can be prepared by the asymmetric hydroboration of cyclohexadiene (Eq. 28). Enantiomerically enriched reagent 24 (94% ee) adds to aldehydes at −78◦ to give the corresponding homoallylic alcohols with high enantioselectivities (94% ee).70 From the useful α-chloro allylic boronates 23 and 28,65 – 67,83,146 a number of other α-substituted reagents can be obtained by nucleophilic substitution of the chloride substituent (Fig. 6). For example, the α-methoxy reagent 7568,147 and αmethyl substituted reagent 2163 – 65 provide excellent enantiofacial discrimination with levels of enantiocontrol over 95% ee. These reagents provide interesting insight into the important steric and electronic factors involved in the allyboration transition structure. For all of these α-substituted reagents, two competing chairlike transition structure models can be proposed where the α substituent is positioned either in a pseudo-equatorial or in a pseudo-axial orientation.146 These two competing structures lead to opposite configurations for the resulting homoallylic alcohols, and their relative energy difference depends on the nature of the substituent on the α-carbon, on the nature of the diol boronate auxiliary, and also on the presence of γ-substituents on the allylic boronate. For example, in reactions with α-chloro reagent 23, the chloroalkenyl homoallylic alcohol product (Z)-78 is largely predominant (>99:1) over the E-configured product 80, and it is obtained in a very high level of enantioselectivity (Scheme 8).65,66 This very high enantioselectivity of the product reflects the high enantiopurity of reagent 23. The predominance of stereoisomer 78 and its Z-olefin geometry can be explained in

Cy O B O

Cy O B O

Cy

O B O

Cl

Cl

O B O

OMe

23

28

B[(–)-Ipc]2

O B

75

21

Ar

24

O

Ar

CO2R 29, 30 Ar = CPh2(OMe)

O

B

O

O

O

OEt

76

Figure 6. Chiral α-substituted allylic boron reagents.

B

O

O B

R 25

O

Cy

34

ORGANIC REACTIONS Cy

R

Cy R Cl 78 R = i-Pr (89%) >99% ee R = Ph (79%) >99% ee

Cl

Cy O B O

OH

O O B O H

Cy

77 favored T.S. +

RCHO

Cl Cy

23

R

O Cl B O O

OH

Cy

Cl

R 80

79

Scheme 8. Stereoinduction model for the additions of chiral α-chloro allylboronate 23.

terms of one preferred transition structure 77 where the chloro substituent adopts a pseudo-axial orientation to minimize dipole repulsion, and to avoid Coulombic repulsions with the oxygen atoms of the boronate. In transition structure 79, unfavorable steric interactions and electronic repulsions are unavoidable between the pseudo-equatorial chloro substituent and the dioxaborolane substituents. It had been shown previously that the 1,2-dicyclohexyl ethanediol (DICHED) auxiliary had little effect on the stereochemical outcome of the reaction.64 Thus, the stereogenic α-chloro center and not the chiral boronate unit is the main contributor to the highly efficient enantiofacial differentiation in these allylations. The size of the boronate auxiliary, however, influences the relative proportions of isomers by further disfavoring transition structures like 79 where the α-substituent occupies the pseudo-equatorial position.148 Reagent 23 also performs very well in double diastereoselection with chiral α-alkoxy aldehydes.65,66 This reagent, prepared as shown in Eq. 27, has a small tendency to isomerize and thus is combined with aldehydes directly. The E-crotylboronate derivatives 28 and 75 behave similarly. As shown in Eqs. 61 and 62, these reagents were successfully tested with simple aliphatic aldehydes and benzaldehyde and provide very high levels of stereoselectivity in the formation of anti-propionate products.67,68 Although the α-methoxy derivative 75 is more diastereoselective, it provides lower enantioselectivity because it can be obtained only in 90% ee from enantiopure 28 via an SN 2 displacement that causes some erosion of the enantiomeric purity. O B O Cl 28 95% ee

OH

RCHO 20°, 12 h

OH +

R

R

Cl

Cl R = Et (47-65%) 95:5 d.r., 96% ee R = Ph (53-68%) 95:5 d.r., 98% ee

(Eq. 61)

ALLYLBORATION OF CARBONYL COMPOUNDS

O B O

OH

RCHO 20°, 12 h

35

OH +

R

OMe

R

(Eq. 62)

OMe

OMe

R = Et (81%) >99:1 d.r., 90% ee R = Ph (79%) >99:1 d.r., 90% ee

epi-75 90% ee

The α-methyl Z-crotylboronate derivative 21 can be obtained in high enantiomeric purity, and its additions to aldehydes are highly diastereoselective and occur with almost perfect enantiofacial selectivity (Scheme 9).63,64 In this instance, the unfavored transition structure 83 (leading to Z-product 84) with the pseudo-axial α-methyl group develops a strong pseudo-1,3-diaxial interaction between the two methyl substituents of the reagent. The favored transition structure 81 is devoid of such an interaction, and provides the E-configured synpropionate adducts 82 with very high stereoselectivity. Reagents 21, 28, and 75 (Fig. 6) have also been used extensively in double diastereoselective synthesis with chiral aldehydes, and they generally lead to high levels of reagent control (see section “Double Diastereoselection”).63,64,67,68,83,149 The enantiomerically pure α-substituted reagents of type 29/30 (Fig. 6, Eq. 39) react with benzaldehyde to give the expected homoallylic alcohol products such as 86 with high enantioselectivity (Eq. 63).85,86 By analogy with the abovedescribed reagents, the addition is presumed to occur through transition structure 85 with the pseudo-axial α-alkyl substituent. The competing transition structure with the pseudo-equatorial substituent would experience severe non-bonding interactions between this group and the bulky boronic ester moiety.

Cy

OH

O O B O

R

Cy

R 82

Cy O B O

81 favored T.S. Cy +

RCHO

R = Et (79%) 98% ee R = Ph (71%) 99% ee

Cy

21

O B O R

OH

Cy R

O 84 83

Scheme 9. Stereoinduction model for the additions of chiral α-methyl crotylboronate 21.

36

ORGANIC REACTIONS R

R O B

O

R

PhCHO, toluene

R

–100° to rt

O O B O H

CO2Et

OH Ph

86 (91%) 96% ee

CO2Et

29 R = CPh2(OMe)

CO2Et

Ph

85

(Eq. 63)

Recently, the first examples of catalytic enantioselective preparations of chiral α-substituted allylic boronates have appeared. Cyclic dihydropyranylboronate 76 (Fig. 6) is prepared in very high enantiomeric purity by an inverse electrondemand hetero-Diels–Alder reaction between 3-boronoacrolein pinacolate (87) and ethyl vinyl ether catalyzed by chiral Cr(III) complex 88 (Eq. 64). The resulting boronate 76 adds stereoselectively to aldehydes to give 2-hydroxyalkyl dihydropyran products 90 in a “one-pot” process.150 – 152 The diastereoselectivity of the addition is explained by invoking transition structure 89. Key to this process is the fact that the possible “self-allylboration” between 76 and 87 does not take place at room temperature. Several applications of this three-component reaction to the synthesis of complex natural products have been described (see section on “Applications to the Synthesis of Natural Products”). The catalytic asymmetric diboration of allenes provides α-substituted 2-boronyl allylic boronates of type 25 (see Eq. 32). One of them, 91, adds to benzaldehyde, albeit with a slight erosion of stereoselectivity (Eq. 65).73 The major β-hydroxy ketone stereoisomer, isolated after an oxidative work-up, originates from the putative chairlike transition structure 92.

Me

N

O

B

O Cr Cl O

O + OEt (solvent)

B(pin) 88 (1 mol%)

RCHO, 45°

4 Å MS, rt, 1 h O

O 87

OEt

76 96% ee

O

(pin)B H H

R O

R OEt

H H 89

HO

H

O

OEt

90 (80-90%) >99:1 d.r., >95% ee

(Eq. 64)

ALLYLBORATION OF CARBONYL COMPOUNDS

O

B

O

O B

O

O O B

1. PhCHO, rt 2. H2O2

Ph 91 87% ee

O B

O Ph

O

O

37

Ph Ph

OH Ph

(56%) 82% ee

92

(Eq. 65) Enantioselective Additions with Chiral Propargyl Reagents As demonstrated by the example in Eq. 66, propargylboron reagent 93 affords allenic alcohols in very high enantioselectivities.153 Although this reagent has not been widely employed, the selectivity it provides with all classes of aldehydes is truly remarkable (>99% ee for model aliphatic, unsaturated, and aromatic aldehydes). Ph

Ts

N Ph B N Ts 93

O n-C5H11

OH

CH2Cl2

+ H

–78°, 2.5 h

n-C5H11

(Eq. 66)

(82%) >99% ee

Enantioselective Additions with Chiral Allenyl Reagents Although they were among the first examples to illustrate the use of tartrate boronate auxiliaries, allenylboronate reagents are seldom employed. The tartratederived reagent 94 provides homopropargylic alcohols in high enantioselectivity from aliphatic aldehydes (Eq. 67).123 This reagent provides optimal selectivity when substituted with the bulkier diisopropyl tartrate ester, and even in this situation aromatic aldehydes react sluggishly and with low stereoselectivity. The efficacy and scope of bis(sulfonamide) allenylboron reagent 95 has been investigated in detail.153 As exemplified in Eq. 68, this reagent adds to most types of aldehydes with high enantioselectivities. A recently described chiral dialkylallenylborane provides comparable selectivities.144 CO2Pr-i O B

O

+ O

R

CO2Pr-i

–78°, 20 h

H

R

(Eq. 67)

R = n-C5H11 (63%) >95% ee R = Ph (43%) 79% ee

94

Ts

OH

toluene

Ph N Ph B N Ts 95

O +

CH2Cl2 H

OH

(Eq. 68)

–78°, 2.5 h (76%) 94% ee

38

ORGANIC REACTIONS

Enantioselective Additions with Chiral 3-Heterosubstituted Reagents A large number of chiral 3-substituted allylic borane and boronate reagents have been described (Fig. 7). To be effective, these reagents must be prepared in geometrically pure form. Like the corresponding crotyl reagents, additions to aldehydes are diastereospecific as the anti/syn configuration of the resulting homoallylic alcohol products is dependent upon the geometry of the original allyl unit. Preparation of 1,2-Diols. The most direct method of preparation of 1,2 diols from allylic boron reagents involves the use of 3-alkoxy-substituted reagents. Although these reagents are prepared easily from the corresponding lithiated 3-alkoxypropene, only the Z-isomers are prepared directly in this fashion as a result of the preference for a cis-configuration in the lithium-chelated allylic carbanion (see Eq. 18, section “Preparation of Allylic Boron Reagents”). The resulting Z-configured reagents provide the syn-1,2-diol products in excellent diastereoselectivity in agreement with the usual cyclic chairlike transition structure. These reagents are very effective in double diastereoselection with α-substituted aldehydes.11 Several chiral analogues such as 14, 96, 97,48,154 and 98,155 are sufficiently effective for use in absolute stereocontrol (Fig. 7). In particular, the bis(isopinocampheyl)-derived 3-alkoxyallylboranes such as 96 react highly enantioselectively with a wide range of aldehyde substrates, including the notoriously troublesome acrolein (Eq. 69).156

O B

B(Ipc)2 RO 14 R = Me 96 R = CH2OMe 97 R = CH2O(CH2)2TMS

O

O

CO2Pr-i

O

O

O B

TBDMSO 98

O

CO2Pr-i

99

CO2Pr-i

O B

B(Ipc)2

(i-Pr2N)Me2Si

100

B(Ipc)2 13

Me Me Si Ar

O B

101 Ar = Ph 102 Ar = B(Ipc)2 Cl

Ar

N

B(Ipc)2

Ar 103

104

Figure 7. Chiral 3-substituted allylic boron reagents.

O

CO2Pr-i

O

ALLYLBORATION OF CARBONYL COMPOUNDS

39

O B[(–)-Ipc]2 MOMO

HO

H

(Eq. 69)

Et2O, –78°

OMOM (66%) 95% ee

96

To access anti-1,2-diols, indirect methods are required for the preparation of geometrically pure, chiral E-3-alkoxy reagents. To this end, the isomerization of alkenylboronic esters described above (Eq. 41), provides a reliable route to tartrate-derived E-3-siloxy allylboronate 99 (Fig. 7). The latter shows variable enantioselectivities in additions to aldehydes, with cyclohexanecarboxaldehyde affording the highest selectivity (Eq. 70).88 CO2Pr-i TBDMSO

O B

O

CO2Pr-i

HO CyCHO, 4 Å MS toluene, –78°, 5 h

Cy

(Eq. 70)

OTBDMS

(R,R)-99

(85%) >99:1 d.r., 91% ee

Alternatively, masked hydroxy groups may be used as the γ-substituent. For example, following allylation with the E-3-boronyl reagent 100 (Fig. 7), the second hydroxy group is generated upon an oxidative work-up that transforms the alkylboronate unit of intermediate 105 with full retention of configuration (Eq. 71).157 Likewise, provided it can be protodesilylated in the presence of an allylsilane moiety, a suitable silyl substituent can be subjected to stereospecific Tamao–Fleming oxidative conditions to afford the desired anti 1,2-diol. The requisite E-3-silyl-substituted reagents are conveniently prepared by trapping of the corresponding allylic carbanions154 with a borate ester (Eq. 17).38 – 40,45,46 Both borane and boronate reagents, exemplified by the respective pinene- and tartrate-derived reagents 1345 and 102158 (Fig. 7, Eqs. 72 and 73), afford diol products in moderate yields but with high enantioselectivies after a stereospecific Tamao–Fleming protodesilylation/oxidation of the β-hydroxy silyl intermediates (e.g., 106). As with other substituted reagents, however, only the bis(isopinocampheyl) allylic boranes 100 and 13 lead to practical levels of enantioselectivity suitable for absolute stereocontrol. Reagent 100, in particular, has found useful application in the synthesis of complex natural products (see section on “Applications to the Synthesis of Natural Products”). [(–)-Ipc]2BO

O

RCHO, Et2O

O B

B[(–)-Ipc]2

–78°, 4 h

H2O2

R O

B

100 105

O

aq NaOH

HO R OH (63-80%) >97.5:2.5 d.r., >90% ee

(Eq. 71)

40

Y

ORGANIC REACTIONS

B[(–)-Ipc]2

[(–)-Ipc]2BO

RCHO

HO H2O2, KF, KHCO3

R

Et2O, –78°

THF/MeOH, rt

R OH

Y

13 Y = SiMe2N(Pr-i)2

(30-63%) >97.5:2.5 d.r., 75-95% ee

106

(Eq. 72) CO2Pr-i O B

Me Me O Si

HO 1. RCHO, toluene, –78°, 5 h

O

(R,R)-102

CO2Pr-i

2. MeCO2H, CH2Cl2 3. H2O2, KF, KHCO3, THF/MeOH, rt

R OH (—) >99:1 d.r., 74-82% ee

(Eq. 73)

Preparation of 1,4-Diols, Epoxides, and Amino Alcohols. Reagent 101 (Fig. 7) illustrates the complications typically encountered in the design of 3-silylsubstituted allylic boron reagents, which require a selective protolytic desilylation of the resulting allylic silane to afford a 1,2-diol product. As opposed to the closely related 2-menthofuryl-derived reagent 102, this selective desilylation is not possible with reagent 101 (Fig. 7). Epoxidation of the aldehyde addition products of allylic silane (R,R)-101 with dimethyldioxirane, however, followed by an acid-catalyzed Peterson rearrangement, provides E-4-hydroxy3-alkenol products 107 in good enantioselectivities (Eq. 74).40 Reagent 101 is also very efficient in double diastereoselection with several types of chiral αsubstituted aldehydes. The Z-3-chloro-substituted bis(Ipc) reagent 103 (Fig. 7), prepared by lithiation of 3-chloropropene, exists in equilibrium with the α-chloro isomer 108 (Eq. 75). Isomer 103, however, adds faster to a wide range of aldehydes to give syn-chlorohydrins 109 with high enantioselectivities.159 The diastereoselectivity is explained by invoking the usual cyclic chairlike transition structure. Treatment of the chlorohydrins under basic oxidative conditions affords synthetically useful vinyl epoxides. Several aldehyde types (aliphatic, aromatic, unsaturated) have been used successfully with reagent 103. A 3-imino reagent of E-geometry, 104, adds to aldehydes to afford anti amino alcohols with good enantioselectivities (Eq. 76).160 However, even the simplest aldehydes tested (benzaldehyde, cyclohexanecarboxaldehyde) give modest yields of products (ca. 50–60%).

CO2Pr-i Me Me Si Ph

O B

O

(R,R)-101

CO2Pr-i

1. RCHO, 4 Å MS, toluene, –78°

HO OH

2. O O, acetone, rt

R

3. AcOH, MeOH

107 (>80%) 81-87% ee

(Eq. 74)

ALLYLBORATION OF CARBONYL COMPOUNDS

B[(–)-Ipc]2

RCHO –95°, 4 h

Cl

HO

O

H2O2, NaOH

R

R (60-65%) >94:6 d.r., 90-97% ee

Cl

103

41

109

B[(–)-Ipc]2 Cl

(Eq. 75)

108 Ar

N

B[(–)-Ipc]2

HO 1. RCHO, –78° 2. H2O2, aq NaOH 3. MeONH3+Cl–

Ar 104

R

(Eq. 76)

NH2 (50-60%) >90% d.r., 90-93% ee

Lewis and Brønsted Acid Catalyzed Enantioselective Additions The recent advent of the Lewis acid catalyzed allylboration reactions opened new doors for enantioselective allylborations and motivated the reexamination of a number of chiral auxiliary systems. In this perspective, reagents 110–112121 are extremely enantioselective at −78◦ in the presence of Sc(OTf)3 as catalyst (Eq. 77).27,28 These hydrolytically stable reagents can be conveniently purified by silica gel chromatography. Consistently high levels of absolute stereoinduction (>95% ee) are observed with a broad range of aldehydes for the unsubstituted allyl reagent 110 as well as the methallyl reagent 111, and both crotyl reagents (E)- and (Z)-112. Although this method requires a stoichiometric amount of the chiral diol auxiliary, this diol is readily recovered after the hydrolytic workup. Aromatic aldehydes and, unless they are very hindered, aliphatic aldehydes (including functionalized ones) react efficiently to give good to high yields of products. Although α,β-unsaturated aldehydes react poorly, acetylenic aldehydes are very competent substrates even with the crotyl reagents 112 (Eq. 78).28 Ph O R1

+ H

R R2

4

Sc(OTf)3 (2-10 mol%)

O B

O H

R3 110 111 (E)-112 (Z)-112

R2, R3, R4 = H R2, R3 = H, R4 = Me R2 = Me, R3, R4 = H R2, R4 = H, R3 = Me

CH2Cl2, –78°

O B

H

R4

R2 O 1 3 Sc(III) R R

H O

113 HO

R4

R1 2 R3 R

(50-95%) >98% d.r., up to 98% ee

(Eq. 77)

42

ORGANIC REACTIONS O

Ph H

+

O

n-C5H11

B

HO

Sc(OTf)3 (2 mol%) CH2Cl2, –78°

O H (E)-112

n-C5H11 (75%) >98% d.r., 96% ee

(Eq. 78) On the basis of mechanistic studies,29 a closed bimolecular transition structure 113 involving activation of the boronate unit via coordination of the scandium to one of the dioxaborolane oxygen atoms has been proposed (Eq. 77). A possible interpretation to explain the enantioselectivity of this allylation system originates from the accepted stereoinduction model for the non-catalyzed reaction arising from a πphenyl -π*C=O attraction.121,161 It has been proposed that the Sc(III) ion coordinates to the least hindered lone pair (syn to H) of the pseudo-equatorial oxygen, thereby suppressing nO -pB conjugation and maximizing boron-carbonyl bonding.29 The real promise of this catalytic reaction is the eventual development of an efficient enantioselective allylboration catalyzed by chiral Lewis acids. A stereoselective reaction using a substoichiometric amount of a chiral director has been reported, but only modest levels of stereo-induction were achieved with an aluminum–BINOL catalyst system (Eq. 79).25 Recently, a chiral Brønsted acid catalyzed system has been devised based on a diol–tin(IV) complex (Eq. 80).162 In this approach, aliphatic aldehydes provide enantioselectivities (up to 80% ee) higher than those of aromatic aldehydes when using the optimal complex 114.163 Although the levels of absolute stereoselectivity of this method remain too low for practical uses, promising applications are possible in double diastereoselection (see section on “Double Diastereoselection”). O B

+

PhCHO

O

toluene, –78°, 6 h

31

HO OH 114 SnCl4 (~10 mol%)

O

+ O

Ph

(Eq. 79)

(40%) 99% d.r., 51% ee

(E)-7

O B

OH

Et2AlCl/(S)-BINOL (10 mol%)

Ph

H

Na2CO3 (0.2 eq), 4 Å MS, CH2Cl2, –78°, 2 h

HO

(Eq. 80)

Ph (85%) 78% ee

A copper-catalyzed reaction using a chiral diphosphine ligand, DuPHOS, with an added lanthanide salt, provides good levels of enantioselectivity (67–91% ee) in additions of the simple allylboronate 31 to both aromatic and aliphatic ketones that present a large difference of steric bulk on the two sides of the carbonyl group.164 One such example is shown in Eq. 81. On the basis of 11 B NMR experiments and on the lack of diastereoselectivity in crotylation reactions, the

ALLYLBORATION OF CARBONYL COMPOUNDS

43

mechanism of this allylation is believed to involve transmetalation of the boron to an allylcopper species. O O B

+

CuF2•2H2O (3 mol%), (R,R)-i-Pr-DUPHOS (6 mol%)

OH

(Eq. 81)

La(OPr-i)3 (4.5 mol%) DMF, –40°, 1 h

O

(87%) 90% ee

31 (1.2 eq)

Double Diastereoselection with Chiral Carbonyl Substrates Double diastereoselective additions between chiral allylic boron reagents and enantiopure chiral carbonyl compounds can be highly advantageous because the resulting diastereomers are separable (in theory, though not always in practice).165 The most desirable situation is where there is very high reagent control to override the intrinsic effect of the stereogenic center of the aldehyde or ketone on the diastereofacial selectivity. The success of this approach depends heavily on the structure of the particular chiral aldehyde used and the nature of its substituents, including protecting groups. Fortunately, the directing effect of the bis(isopinocampheyl) allylic boranes is extremely powerful, giving rise to high reagent control in double diastereoselective additions. As demonstrated with the simple allylations of chiral, α-substituted aldehydes 39 and 115, reagentcontrolled additions are very effective (Eqs. 82–85).166 Both examples involving aldehyde 39 (Eqs. 82 and 83) are very favorable in comparison to the modest selectivity of the achiral pinacol allylboronates (compare to Scheme 2). Reagent control is observed even in mismatched situations such as the difficult case of α-phenyl aldehyde 115 (Eq. 85).166,167 B[(+)-Ipc]2 64

OH

OH +

(Eq. 82)

THF, –78°, 3 h O (83%) 5:95 d.r. H B[(–)-Ipc]2 64

39

OH

OH +

(Eq. 83)

THF, –78°, 3 h (81%) 96:4 d.r. B[(+)-Ipc]2 64

OH

(Eq. 84)

+

THF, –78°, 3 h

O

Ph

Ph (78%) 2:98 d.r.

H Ph 115

OH

B[(–)-Ipc]2 64

OH

OH +

(Eq. 85)

THF, –78°, 3 h Ph

Ph (74%) 67:33 d.r.

44

ORGANIC REACTIONS

By using a judicious combination of the appropriate double bond geometry and pinene enantiomer, the corresponding crotylboranes present a very nice solution to the problem of full stereocontrol of acyclic dipropionate units when combined with chiral α-methyl β-alkoxy aldehydes such as 116 (Eqs. 86–89).167 In this situation as well, reagent-controlled additions are very selective even in mismatched cases, affording stereotriads in high yields and >90% d.r. Simple α-alkoxy aldehydes provide comparable levels of selectivites but exceptions have been reported with stereogenic β-alkoxy centers and more complex aldehydes.168 B[(+)-Ipc]2

OH

(E)-12 THF, –78°, 3 h

(Eq. 86)

BnO (84%) 95:5 d.r.

B[(–)-Ipc]2 OH

(E)-12 THF, –78°, 3 h

(Eq. 87)

BnO

O (87%) 98:2 d.r.

BnO

H B[(+)-Ipc]2 116

OH

(Z)-12 THF, –78°, 3 h B[(–)-Ipc]2

(78%) 95:5 d.r. OH

(Z)-12 THF, –78°, 3 h

(Eq. 88)

BnO

BnO

(Eq. 89)

(83%) 92:8 d.r.

In comparison, additions of chiral allylic boronates such as tartrate-based reagents tend to be less selective in double diastereoselective additions to α-methyl aldehydes, especially in mismatched cases (Eqs. 90–92).169 Nonetheless, these reagents are advantageous as they can increase, even in the mismatched manifold, the intrinsic levels of selectivities dictated by the chiral aldehyde substrate, and the resulting diastereomeric products are usually separable by chromatography. When used with α-alkoxy aldehydes such as glyceraldehyde acetonide (51, Scheme 4), tartrate-based reagents are highly effective.126,170 Several applications of double diastereoselective additions of tartrate-based allylic boronate reagents have been described in the course of the synthesis of complex natural products (see section on “Applications to the Synthesis of Natural Products”).

ALLYLBORATION OF CARBONYL COMPOUNDS

O BO (Z)-7

OH

toluene, rt

RO

OH +

RO

syn-syn

(—) 55:29 anti-syn:syn-syn + other diastereomers (16%)

CO2Pr-i O B O CO2Pr-i

H

117 R = TBDMS

(Eq. 90)

RO

anti-syn

O

45

(S,S)-(Z)-11 toluene, –78° (R,R)-(Z)-11 toluene, –78°

(71%) 95:1 anti-syn:syn-syn + other diastereomer (4%)

(Eq. 91)

(—) 45:41 anti-syn:syn-syn + other diastereomers (14%)

(Eq. 92)

The use of chiral Brønsted acids is illustrated in Eq. 93 as a method for catalyst-controlled double diastereoselective additions of pinacol allylic boronates.163 Aside from circumventing the need for a chiral boronate, these additions can lead to very good amplification of facial stereoselectivity. For example, compared to both non-catalyzed (room temperature, Eq. 90) and SnCl4 catalyzed variants, the use of the “matched” diol-SnCl4 enantiomer at a low temperature leads to a significant improvement in the proportion of the desired anti-syn diastereomer in the crotylation of aldehyde 117 with pinacolate reagent (Z)-7 (Eq. 93). Moreover, unlike reagent (Z)-11 (Eq. 91) none of the other diastereomers arising from Z- to E-isomerization is observed.

O TBDMSO 117

H

O B

+

HO O

OH [(R,R)-diol]

SnCl4 (10 mol%), Na2CO3 (0.2 eq) toluene, –78°, 24 h

(Z)-7 OH TBDMSO

OH +

TBDMSO syn-syn

anti-syn Conditions SnCl4 alone SnCl4, (R,R)-diol (11 mol%) SnCl4, (S,S)-diol (11 mol%)

(81%) (77%) (50%)

anti-syn:syn-syn 66:34 95:5 68:32

(Eq. 93)

46

ORGANIC REACTIONS

The chiral α-substituted reagents 21, 23, 28, and 75 (Fig. 6) are very powerful controllers of double diastereoselective additions and perform admirably well even in mismatched situations.63 – 66,68,83,147,149 Reagent 75 tends to be more selective than the α-chloro analog 28, and the high stereocontrol displayed by reagent 75 in the examples of Eqs. 94 and 95 can be explained using a transition structure model similar to that of Scheme 8.68,147 Remarkably, even the mismatched pair (Eq. 95) affords outstanding selectivity. Several other examples have been described, including applications to the synthesis of complex polypropionate natural products (see section on “Applications to the Synthesis of Natural Products”: Scheme 19). O BO OMe (R)-75

OH

OH

toluene, –78° to rt, 60 h

OMe

OMe syn-anti

O

(Eq. 94)

+

anti-anti

(59%) >95:5 syn-anti:anti-anti H

O BO

39

OMe (S)-75 toluene, –78° to rt, 60 h

(Eq. 95)

(—) 5:>95 syn-anti:anti-anti

Intramolecular Reactions Intramolecular additions generally follow the same trends of stereoselectivity as observed in the bimolecular reactions.80,82,171,172 For example, allylic boronates (E)- and (Z)-118 provide the respective trans- and cis-fused products of intramolecular allylation.173 As shown with allylboronate (E)-118, a Yb(OTf)3 catalyzed hydrolysis of the acetal triggers the intramolecular allylboration and leads to isolation of the trans-fused product 119 in agreement with the usual cyclic transition structure (Eq. 96). CH(OMe)2

O

O B O (E)-118

H

Yb(OTf)3 H2O, CH3CN, 90°, 2 h

O

O O B O

OH O

H

119 (77%) >92% trans

(Eq. 96) Intramolecular allylations can also provide five-membered rings with ease, and the entropic benefits facilitate additions to ketone substrates. For example, the allylic boronate 121, formed by a Negishi-type coupling between alkenyl

ALLYLBORATION OF CARBONYL COMPOUNDS

47

bromide 120 and a methylzinc dialkoxyboron reagent, cyclizes in situ into a cyclopentanone to provide a [3.3.0] bicyclic alcohol product (Eq. 97).174 This example constitutes a formal 5-exo-trig cyclization, and seven-membered ring systems can also be elaborated using a similar approach.79,80,174 O IZnCH2B O (1.5 eq)

O Br CO2Et 120

Pd(OAc)2 (3 mol%), Ph3P (9 mol%), benzene, 70°, 3 h

OH

O

O B

O

CO2Et

CO2Et (71%)

121

(Eq. 97) Reagents for Multiple Additions A tandem double-allylation strategy, based on the E-3-boronyl allylborane reagent 100,157 has been optimized for the synthesis of 1,5-diol products from two different aldehyde substrates.175 Specifically, reagent 100 undergoes allylation with a limiting amount of an aldehyde, R1 CHO, and the resulting α-substituted allylboronate 122 can then add to a second added aldehyde (R2 CHO) (Eq. 98). The first allylation with the bis(isopinocampheyl)allylic borane unit is highly enantioselective and the resulting configuration of 122 controls the fate of the second allylation. Thus, from intermediate 122, transition structure 123 featuring a pseudo-equatorial α-substituent explains the stereocontrolled formation of 1,5diol 124. The lower reactivity of 122 compared to 100, as well as a tight control of reagent stoichiometry, helps to minimize the formation of the double allylation product of the first aldehyde (R1 CHO). [(–)-Ipc]2BO

O

1

R CHO (0.54 eq)

O B

B[(–)-Ipc]2

R2CHO

R1

Et2O, –78°, 2 h

O

B

O

rt, 24 h

100 122 [(–)-Ipc]2BO O R1 B O O 2 R 123

work-up

HO 1

R

(Eq. 98) OH R2

124 (65-87%) up to 96% ee

With the analogous reagent 125, however, the corresponding allylboronate intermediate 126 is thought to favor a transition structure 127 where the α-substituent is positioned in a pseudo-axial orientation in order to escape nonbonding interactions with the bulky tetraphenyl dioxaborolane (Eq. 99). This way, a Z-configured allylic alcohol unit of opposite configuration is obtained in diol product 128. This type of steric control with chiral α-substituted allylboronates

48

ORGANIC REACTIONS

had been demonstrated before (see section on α-substituted reagents). The usefulness of this powerful tandem allylation/allylation strategy is demonstrated by the preparation of several examples of both types of 1,5-diols 124 and 128, and by a number of successful applications to the synthesis of complex natural products (see section on “Applications to the Synthesis of Natural Products”). [(–)-Ipc]2BO Ph

Ph O Ph B Ph O

R1

R1CHO (0.82 eq)

O

Et2O, –78°, 2 h

B[(–)-Ipc]2

Ph

125

B

R2CHO rt, 24 h

O

Ph Ph

Ph

126

Ph Ph Ph

Ph

O

OH

O B

work-up O

[(–)-Ipc]2BO

HO R2 R1

127

R2

R1 128 (72-95%) up to 95% ee

(Eq. 99) A double Brown-type allylation reagent, 129, gives C2 -symmetric 3methylenepentane-1,5-diols 130 in modest yields but high enantioselectivities with both aliphatic and aromatic aldehydes (Eq. 100).176 This reagent can be prepared by double deprotonation of 2-methylpropene followed by condensation with either antipodes of (Ipc)2 BCl. For example, (S,S)-129 originates from [(+)-Ipc]2 BCl. Double allylboration of an excess of aldehyde with (S,S)-129 affords C2 -symmetric diol product 130 accompanied with approximately 5–15% proportion of “monoallylboration” alcohol after the oxidative work-up. 1. RCHO (2-3 eq), Et2O, –78°, 3 h [(+)-Ipc]2B

B[(+)-Ipc]2 (S,S)-129

2. H2O2, aq NaOH

HO R

OH R

(Eq. 100)

130 (38-55%) >95% ee

Tandem Reactions Many of the recent advances in synthetic applications of allylic boron reagents have focused on the use of these reagents as key components of tandem reactions and “one-pot” sequential processes, including multicomponent reactions. The following examples briefly illustrate the range of possibilities. Most cases involve masked allylboronates as substrates, and the tandem process is usually terminated by the allylboration step. Intramolecular Allylboration. In one rare but impressive example involving a masked aldehyde, a domino hydroformylation/allylboration/hydroformylation reaction cascade has been designed to generate bicyclic annulated

ALLYLBORATION OF CARBONYL COMPOUNDS

49

tetrahydropyrans177 and nitrogen heterocycles.178,179 For example, treatment of allylboronate 131 under hydroformylation conditions first leads to aldehyde intermediate 132 (Eq. 101). With a poised allylic boronate, formation of 132 triggers the key intramolecular allylation to give intermediate 134.179 This intermediate then undergoes a second hydroformylation, followed by a final cyclization to give the bicyclic lactol product 135 in 83% yield as a 1 : 1 mixture of anomers. The final products are obtained in this one-pot process with a very high diastereoselectivity (97 : 3 ratio) as a result of simple diastereocontrol in the allylboration step involving the putative transition structure 133. Similar approaches are employed to access pyran derivatives.177

N

B O

Ts

Rh(CO)2(acac) (1 mol%), biphephos (2 mol%)

O

O N

H2/CO (5 bar), THF, 60°, 4 d

B(pin)

Ts

131

132 H

H

OH

O

OH

O

Ts N

B(pin) H

N H Ts

133

134

N H Ts 135 (83%) 97:3 d.r.

(Eq. 101) A masked allylic boron unit can be revealed through a transition-metalcatalyzed borylation reaction. For example, a one-pot borylation/allylation tandem process based on the borylation of various ketone-containing allylic acetates has been developed.180 The intramolecular allylboration step is very slow in DMSO, which is the usual solvent for these borylations of allylic acetates (see Eq. 33). The use of a non-coordinating solvent like toluene is more suitable for the overall process provided that an arsine or phosphine ligand is added to stabilize the active Pd(0) species during the borylation reaction. With cyclic ketones such as 136, the intramolecular allylation provides cis-fused bicyclic products in agreement with the involvement of the usual chairlike transition structure, 137 (Eq. 102). O CO Et 2

O + O

136

O

Pd(dba)2 (6 mol%), AsPh3 (6 mol%)

O

toluene, 50°, 16 h; 100°, 24 h

B B

OAc

1.1 eq

(Eq. 102) CO2Et O O B O 137

OH

CO2Et (72%)

50

ORGANIC REACTIONS

Intermolecular Allylboration. A tandem aza[4+2] cycloaddition/allylboration three-component reaction181,182 has been designed based on the precedented carbocyclic [4+2] cycloaddition/allylboration89 and a subsequent one-pot variant.183 Thus, the thermal reaction between hydrazonobutadienes 138, N -substituted maleimides, and aldehydes provides polysubstituted α-hydroxyalkylpiperidines 141 via the cyclic allylboronate intermediate 139 and the proposed chairlike transition structure 140 (Eq. 103).181 Monoactivated dienophiles like acrylates fail to react with heterodienes 138 but the scope of aldehydes is very broad; both aliphatic and aromatic aldehydes are suitable, including electron-rich ones.182 An inverse electron-demand variant to access the corresponding dihydropyran derivatives via the intermediacy of enantiomerically enriched pyranyl allylic boronate 76 has been subsequently developed (see Eq. 64).150 – 152

O

B

O

O +

NR

O 3

O

+ R4

toluene H

O

80°, 3 d

NR3

O

N

O

B

N NR1R2

NR1R2 138

O

139 O O O O B 3 R4 NR N H O H H NR1R2 H H

O R4 HO

NR3 N NR1R2

O

141 (50-75%) >97.5:2.5 d.r.

140

(Eq. 103) As described above in Eq. 43, simple allylboronates can be transformed into more elaborated ones using olefin cross-metathesis.184 Treatment of pinacol allylboronate 31 with a variety of olefin partners in the presence of Grubbs’ second-generation catalyst 142 smoothly leads to formation of 3-substituted allylboronates 143 as cross-metathesis products (Eq. 104). Unfortunately, these new allylic boronates are formed as mixtures of geometrical isomers with modest E/Z selectivity. They are not isolated but rather are treated directly with benzaldehyde to give the corresponding homoallylic alcohol products in good yields (Table A). Mes N

O B O 31

+ R

N Mes Cl Ru Ph PCyCl 3 cat. 142 (5 mol%) CH2Cl2, 40°

R

O B O 143

PhCHO rt

OH Ph R (44-79%)

(Eq. 104)

ALLYLBORATION OF CARBONYL COMPOUNDS

51

Table A. Functionalized homoallylic alcohols from olefin cross metathesis and subsequent allylboration reactions with benzaldehyde Cross Partner

Entry

Product

Yield

d.r.

(73%)

3.8:1

(78%)

4.9:1

(58%)

>20:1

(66%)

—

(60%)

>20:1

OH 1

Cl

Ph

Cl Cl

OH 2

Br

Ph

Br Br

OH Ph

3 OH

OH OH

4

Ph OH

5

Ph Br

Br

The main advantage of this one-pot sequence is that it is exceptionally tolerant of sensitive functional groups. Entry 3 (Table A) shows an example with an unprotected alcohol, and entries 1, 2, and 5 all show examples with halogenated groups that are delivered directly from an allylboronate intermediate. These groups, which would not survive the strongly basic conditions or the active metals used in many other preparative methods, are carried through this procedure without incident. Entry 4 is also noteworthy because it shows that quaternary carbon centers can be made with this tandem process. A serious limitation of this approach, however, is that the diastereoselectivity seen in the formation of allylation products is quite variable as a consequence of the low geometric (E/Z) selectivity in the cross-metathesis. Olefin partners with large allylic substituents (entries 3–5) react to give exclusively the anti product shown in Table A. Unfortunately, olefins with smaller substituents (entries 1 and 2) show a much lower preference. Furthermore, both E- and Z-olefins afford the same stereoisomer (compare entries 1 and 2). A mild one-pot procedure based on a platinum-catalyzed diborylation of 1,3butadienes (see Eq. 30) gives doubly allylic boronate 144, which adds to an aldehyde to form a quaternary carbon center in the intermediate 145 (Eq. 105).185 The use of a tartrate auxiliary in this process leads to good levels of enantioselectivity in the final diol product, which is obtained after oxidation of the primary alkylboronate intermediate. Although examples of aliphatic, aromatic, and unsaturated aldehydes have been described, enantioselectivities vary widely (33 to 74% ee), and are good only for aliphatic aldehydes. An intramolecular variant of this interesting tandem reaction is also known.186

52

ORGANIC REACTIONS

EtO2C

O

EtO2C

O

O

CO2Et

O

CO2Et

Pt(dba)2 (2.5 mol%), PCy3 (2.5 mol%)

+

B B

benzene, rt, 12 h

[(L)-tart]B

B[(L)-tart] 144

add 4 Å MS, toluene, –78°;

[(L)-tart]BO

HO NaOH, H2O2

add CyCHO, 3 h

50°, 3 h B[(L)-tart]

OH (72%) >19:1 syn:anti, 74% ee

145

(Eq. 105) The diboration of allenes can also be employed in a similar tandem process. By taking advantage of an improved, more enantioselective variant for the preparation of allylboronates of type 25 (Eq. 32), a one-pot sequence involving allene diboration, aldehyde allylation, and Suzuki cross-coupling has been developed (Eq. 106). It is noteworthy that no change of solvent, nor any addition of palladium catalyst is needed in the last stage involving the cross-coupling of alkenylboronate intermediate 146 to give final product 147.187 Ar Ar O O

O

O B B

O

O

P NMe2 O O Ar Ar (6 mol%)

+

Pd2(dba)3 (2.5 mol%), toluene, 22°, 10 h

C10H21-n

(pin2B2)

Ar = 3,5-Me2C6H3

(pin)BO

B(pin) B(pin)

B(pin)

R 25 R = n-C10H21

HO

Ph

PhI, KOH

i-PrCHO C10H21-n 146

95°

C10H21-n 147 (79%) 88% ee

(Eq. 106) APPLICATIONS TO THE SYNTHESIS OF NATURAL PRODUCTS

Enantioselective Additions The bis(isopinocampheyl)borane reagents described in the sections on enantioselective additions have found extensive use in the total synthesis of complex, bioactive natural products. A synthesis of the potent anticancer agent epothilone

ALLYLBORATION OF CARBONYL COMPOUNDS

53

O

OH H

S

+

B[(–)-Ipc]2

N 148

O

Et2O –100°, 0.5 h

S N (96%) >97% ee

64

O H

149

+

B[(–)-Ipc]2

O

Et2O

OH

–100°, 0.5 h

64

(74%) >98% ee O S

HO

N O O

OH O

epothilone A

Scheme 10

exemplifies particularly well the suitability of the Brown allylation with highly functionalized and hindered aldehydes (Scheme 10). Thus, using the salt-free, low-temperature conditions, reagent 64 is added to unsaturated heterocyclic aldehyde 148 to afford the desired secondary homoallylic alcohol in very high yield and excellent enantioselectivity. The synthesis also featured another Brown allylation on the hindered α-dimethylated β-keto aldehyde 149, thus providing two of the key fragments necessary to assemble the structure of the anticancer agents epothilones.188 The applicability of the bis(isopinocampheyl) reagents is not limited to simple allylations and crotylations. For example, reagent 97 affords syn vicinal diols in very high enantioselectivity (Scheme 11).189 Compared with reagents 14 and 96 (Fig. 7), reagent 97 possesses the added advantage of yielding the alcohol product with an easily removable (2-trimethylsilylethoxy)methyl (SEM) protecting group. In this example, the resulting monoprotected diol has been subsequently converted into the eight-membered ring ether laurencin. With only a small number of substrate types are the tartrate-based allylic boronate reagents enantioselective enough for applications in the control of

B[(–)-Ipc]2

1. EtCHO, –100° to rt 2. aq NaOH, H2O2

OSEM 97

OH OSEM (79%) >95% ee

Br O AcO

H

(+)-laurencin

Scheme 11

54

ORGANIC REACTIONS CO2Pr-i OHC

CHO Fe(CO)3

+

150

O B

4 Å MS

CO2Pr-i O (S,S)-(E)-11

toluene, –78°

H

OH (MeO)2HC H OHC

H

Fe(CO)3

H

OHC as-indacene unit of ikarugamycin

151 (90%) >98% ee

Scheme 12

absolute stereochemistry. One such example involves iron dienyl complexes such as the dialdehyde 150, which reacts with crotylboronate reagent (E)-11 to give the anti-propionate product in the form of complex 151 in over 98% ee (Scheme 12). After a few transformations and decomplexation, the resulting diene is further elaborated into a triene precursor that undergoes an intramolecular Diels–Alder reaction leading to the tricyclic core of ikarugamycin.190 The Corey allylation system based on a chiral bis(sulfonamide) auxiliary was put to use with success in a number of synthetic efforts, including the total synthesis of the anticancer agent leucascandrolide (Scheme 13).191 Chiral reagent 152 is added to an achiral aldehyde, 3-(p-methoxybenzyloxy)propanal, affording intermediate 153 in high stereoselectivity. The latter is transformed into a pyranyl aldehyde, which is subjected to a second allylation (this time, a doubly diastereoselective addition) en route to the completion of leucascandrolide. Double Diastereoselection The powerful directing effect of bis(isopinocampheyl) allylic boranes has been put to great use in the context of several applications of double diasterereoselective allylations in the total synthesis of natural products. As discussed in a previous section, the Brown allylation can be exploited to overcome the stereodirecting effect of chiral α-stereogenic aldehydes, including α-alkoxy substituted ones. Thus, the simple allylation of aldehyde 154 provides as major product the desired diastereomer needed towards a total synthesis of brasilenyne (Scheme 14).192 The yield and stereoselectivity is even increased to over 97 : 3 under the low-temperature, magnesium-free conditions described before.139 A synthesis of the naturally occurring phosphatase inhibitor calyculin C showcased several other interesting examples of doubly diastereoselective additions involving the Brown reagents.168 The addition of tetrasubstituted reagent 155 to 2,3-O-isopropylidene-D-glyceraldehyde (51) provides intermediate 156 in very high selectivity despite a substrate-reagent mismatch, which is overruled by the borane reagent (Scheme 15). The latter is transformed in several steps into aldehyde 157, and a crotylboration of this β-alkoxy aldehyde provided a very high diastereoselectivity for the desired anti-propanoate unit. With the subsequent aldehyde intermediate 158, a third example involves a difficult mismatched case that

ALLYLBORATION OF CARBONYL COMPOUNDS

55

Ts

S

Ph N Ph B Br N Ts rt, 10 h

OR

S

Ts S

OR

N B

S

Sn(Bu-n)3 R = TBDMS

152

Ph

N Ts

O

PMBO

Ph

H CH2Cl2, –78°, 1.5 h

Ts

Ph N B Ph N Ts

S

OR

RO

OH

S

OPMB O

153 (100%) 11:1 d.r.

H H

CH2Cl2, –78°, 1.5 h

O H OPMB

O N

O H

O

OR

O NHCO2Me

H OPMB

HO

O

H

H O

MeO O RO

OR

O

H

(96%) 8.5:1 d.r.

leucascandrolide

Scheme 13 I

O H

O

I

OH +

B[(+)-Ipc]2 64

1. Et2O, –78°, 2 h

O

2. aq NaOH, H2O2

OPMB

OPMB (72%) 93:7 d.r.

154

(89%) >97:3 d.r. when Mg2+ free at –100° HO O

(+)-brasilenyne

Scheme 14

56

O

ORGANIC REACTIONS

O

THF

B[(+)-Ipc]2

+

O

O

–78°

CHO 51

HO

155

156 (73%)

OTBDMS

MEMO O OHC

O

OTBDMS

MEMO

B[(+)-Ipc]2 (E)-12

O O

THF, –78°

OMe

OH OMe OBz 157

OBz (55%) >99:1 d.r.

OTBDMS

MEMO

B[(+)-Ipc]2 (E)-12

O

two steps OHC

O

THF, –78°

OBz OMe OBz 158 OTBDMS

MEMO O O HO

(39%)

O

+

OBz OMe

OTBDMS

MEMO O HO

OBz OMe

OBz

OBz (35%)

calyculin C

Scheme 15

provides an unusually low level of diastereoselectivity (almost 1 : 1), indicating that high selectivity is never guaranteed even with the bis(isopinocampheyl) allylic boranes. In this example of an α-methyl-β-alkoxy aldehyde, reagent control by crotylborane (E)-12 is overruled by the substrate and it was found that the nature of the protecting group on the β-hydroxy substituent is crucial, with the most favorable group a benzoyl. The minor diastereomer of this mismatched double diastereoselective addition possesses the requisite configuration for completing the synthesis of calyculin C. Several allylic boron reagents have been recently employed in a series of doubly diastereoselective additions toward a synthesis of mycalamide.193,194 Thus,

ALLYLBORATION OF CARBONYL COMPOUNDS

57

CO2Pr-i O B

E

O CO2Pr-i (R,R)-159

Et Et O O

H

4 Å MS, toluene, –78°

Et Et O O

two steps

Et Et O O

E

O O Et O Et

HO

160 E = CO2Pr-i

161 (79%) >99:1 d.r.

H

CHO

O B O

B[(+)-Ipc]2 64

Et Et O O

Et2O, –95°

CHO

MeO

MeO

OH

163 (89%) >98:2 d.r.

162

CO2Pr-i TMS

O H

O MeO

O

O Troc

O B

O CO2Pr-i (R,R)-165

4 Å MS, toluene, –78°

OH O TMS MeO

O

O

O Troc

O

166 (93%) >98:2 d.r.

164

OH 1. O O , KHCO3, acetone 2. MeOH, HOAc, rt

O OH

MeO

O

O Troc

(89%)

mycalamide A trioxadecalin unit

O

Scheme 16

the addition of tartrate-derived reagent 159 to 2,3-O-isopropylidene-D-glyceraldehyde provides diastereomer 161 with very high selectivity (Scheme 16). This result contrasts with the formation of 156 using a bis(isocampheyl)-borane reagent (Scheme 15). As described in a previous section, double diastereoselective additions of allylic boron reagents to the glyceraldehyde acetals usually proceed with high selectivity in both matched and mismatched cases due to the lack of a strong bias among the four main rotamers in the transition structures minimizing syn-pentane interactions (see Scheme 4). Unlike the additions of crotyl reagents (see Schemes 2 and 3), transition structures from additions of 3,3-disubstituted reagents cannot escape from syn-pentane interactions and all four of the structures of Scheme 4 display one such interaction between a methyl group and the dioxolane ring. Thus, as substrate control is somewhat mitigated in these instances,

58

ORGANIC REACTIONS

reagent control is more effective, which explains the formation of epimeric alcohols with a judicious choice of the right enantiomer of reagents 155 or 159. In the formation of product 161 from reagent (R,R)-159, the stereoselectivity of this matched manifold can be explained by a Felkin–Anh transition structure 160. Such double diastereoselective additions between tartrate-derived reagents and glyceraldehyde ketals usually proceed with very high stereoselectivity.170 The intermediate 161 is transformed into the hindered α-dimethylated aldehyde 162, which undergoes another doubly diastereoselective addition with Brown’s reagent 64 that results in stereomerically pure product 163. The corresponding tartratederived reagent [(S,S)-53, Fig. 4] gives a much lower selectivity with the same aldehyde. Further transformations of the intermediate 163 leads to α-methoxy aldehyde 164, whose reaction with E-3-trimethylsilyl tartrate reagent 165 (similar to reagent 101, Fig. 7) occurred with high selectivity in the matched manifold to give product 166. The stereoselectivity of this addition can be explained by minimization of syn-pentane interactions just as observed with an E-crotyl reagent (see structure 40 in Scheme 2). As with reagent 101 (see Eq. 74), the allylsilane unit of 166 is oxidized with rearrangement to give an advanced intermediate towards mycalamide A. As demonstrated in the course of a total synthesis of the macrolide bafilomycin,195 double diastereoselective additions can be useful even in the mismatched manifold. For example, the crotylation of chiral α-substituted aldehyde 167 with (E)-11 affords an 85 : 15 ratio of diastereomers favoring the desired anti-anti product (Scheme 17). Without a chiral tartrate reagent, the undesired anti-syn diastereomer would be intrinsically favored from aldehyde 167. The use of the appropriate tartrate reagent, the (R,R) unit in this instance, overturns this preference to afford an acceptable ratio of the two separable diasteomers. Although the class of bis(isopinocampheyl)allylboranes often leads to better levels of double diastereoselectivity, the basic oxidative work-up required in these allylations is not compatible with all substrates. This is true for the crotylation of the aldehyde derived from the terminal alkene of 168 (Scheme 18),

CO2Pr-i

O H

PMBO

O B

+

CO2Pr-i

O

–78°, 8 h

(R,R)-(E)-11

167

OH PMBO

4 Å MS, toluene

4

3

OH +

PMBO 3,4-anti-4,5-syn (—)

3,4-anti-4,5-anti (70%) 85:15

Scheme 17

(–)-bafilomycin A1

ALLYLBORATION OF CARBONYL COMPOUNDS

59

E OPMB

1. OsO4, NMO 2. NaIO4

OAc

3. DEIPSO

O

CO2Pr-i O B

H

R H

O CO2Pr-i (S,S)-(E)-11

168

O O B

E

AcO 169 E = CO2Pr-i

OH

OPMB

O OAc

OH O

OMe O

O

O

O DEIPSO

OH

HO

13-deoxytedanolide

170 (68%, 3 steps)

Scheme 18

which requires the use of boronate (E)-11 because of the milder hydrolytic workup associated with this class of reagents.196 This matched case of double diastereoselection is very efficient, giving intermediate 170 as the exclusive diastereomer, which was further elaborated to reach the targeted natural product, 13-deoxytedanolide. The high stereoselectivity in favor of the Felkin product 170 can be explained through chairlike transition structure 169 using the same stereoinduction model described in Scheme 2, with the largest chain (R) occupying the “outside” position. As demonstrated in a total synthesis of the denticulatins A and B, the class of chiral α-substituted allylic boronates is very effective in double diastereoselection (Scheme 19).197 From aldehyde 171, a simple E-crotylation provides the Felkin product 173. The high stereoselectivity of this crotylation can be explained by invoking transition structure 172 using the same model described in Scheme 2, which minimizes syn-pentane interactions with the largest of the three α-substituents positioned at the outside. Intermediate 173 is then transformed into aldehyde 174, which is subjected to another E-crotylation, however this time with α-methoxy reagent 75. The use of reagent 75 is necessary to optimize the diastereomeric ratio in favor of the desired anti-Felkin stereoisomer 175, which results from a mismatched situation. Thus, the 4 : 1 diastereoselectivity of this reagent-controlled addition is remarkable as additions to α-methyl β-branched aldehydes like 171 and 174 intrinsically favor the Felkin product (e.g., 173 from 171). Here, the stereocontrolling effect of reagent 75 is powerful enough to reverse this trend and to favor diastereomer 175. The latter cyclizes spontaneously into a hemiketal intermediate en route to the synthesis of the denticulatins A and B.

60

ORGANIC REACTIONS

O B TBDMSO

O

O

O O B

(E)-7 H

pet. ether, rt, 14 h

O

H

R H

171 172

O B

TBDMSO

OH

O

173 (95%) 95:5 d.r.

O

OPMB CHO

O OMe 75 toluene, 4 bar

174

O

PMB OH

O

O

PMB OH

+ OMe anti-Felkin product 175

HO

O

H

OMe 4:1 d.r.

Felkin product

OMe denticulatins A and B

OPMB (60%)

Scheme 19

Tandem Reactions Allylic boronates are very suitable for the design of tandem reactions that can be applied in natural product synthesis. Using the strategy illustrated in Eq. 64, an inverse electron-demand hetero-Diels–Alder reaction between 87 and a 2-substituted enol ether, catalyzed by chiral Cr(III) complex 88, leads in high enantioselectivity to cyclic dihydropyranyl boronate 176 (Scheme 20).198 The latter adds stereoselectively, in a one-pot sequential process, to unsaturated aldehyde 177 to give 2-hydroxyalkyl dihydropyran product 178. Interestingly, the large, chiral catalyst 88 promotes the cycloaddition of the requisite Z-enol ether faster than that of the corresponding E-isomer. The remarkable selectivity of this tandem

ALLYLBORATION OF CARBONYL COMPOUNDS

61

O

N

O

B

O Cr O Cl

O

110°, 36 h OEt

O

1.5 eq

(pin)B

O 177

neat, 20°, 5 h

OEt O 87

B(pin)

88 (3 mol%)

+

H

EtO

176

O OEt R2

O

R1

EtO

O

HO

R1 = CH2CH=CMe2 R2 = (E)-MeC=CHCO2Et

H

OEt

O

178 (76%) 98% d.r., 95% ee

OH

OH

HO O HN

O

H N

O O

HO

H

O

thiomarinol H

Scheme 20

reaction allowed an expedient enantioselective synthesis of a potent antibiotic of the thiomarinol family. A related aza[4+2] cycloaddition/allylboration has been applied to the enantioselective synthesis of palustrine alkaloids.199,200 The double allylation reagent 125 described in a previous section (see Eq. 99) has been put to use with remarkable efficiency in the context of natural product synthesis. In the construction of the pyran-containing C43-C67 fragment of the complex marine natural product amphidinol 3, a one-pot double allylation with two different acetonide-protected chiral α-substituted aldehydes is performed (Scheme 21).201 The first allylation involved a stereochemically mismatched case of double diastereoselection, which is resolved by the strong directing power of the bis(isopinocampheyl)boryl unit and the optimal choice of protecting group. The desired intermediate 179 then reacts with the second aldehyde to give product 180 in high yield and with good overall stereoselectivity (9 : 1 d.r.). Functional group manipulations and a subsequent cyclization afford the pyran core of amphidinol 3. Reagent 125 is also used in the construction of the C1C25 fragment of the same natural product.202 The related reagent 100 (see Eq. 98) has been put to use toward the synthesis of peloruside.203

62

ORGANIC REACTIONS

TBDPSO TBDPSO

O

Ph

Ph O + Ph B Ph O

H

O O

CH2Cl2 B[(+)-Ipc]2

OH

O O

–78°

O Ph

125

B

O

Ph Ph

Ph

179 O H

O O

OH TBDPSO

OH

HO

TBDPSO HO

O O

CH2Cl2, rt

O

O O

H

O

180 (70-80%) 9:1 d.r.

O

H

O O

pyran core of amphidinol 3

Scheme 21

Transformations of Residual Groups The residual alkenyl unit obtained in the products of addition of allylic boron reagents offers myriad possibilities for further derivatization in the synthesis of natural products. For instance, earlier sections (see sections on Preparation of 1,2-Diols, and 1,4-Diols) describe oxidative processes involving allylic silane units originating from additions of 3-silyl-substituted reagents. With the recent advent of alkene metathesis reactions, the possibilities of manipulations of the residual alkenyl unit have grown further. One attractive application in the synthesis of γ-lactones is exemplified in a synthesis of goniothalamin.204 Thus, a simple allylation of cinnamaldehyde followed by acryloylation provide intermediate 181 (Scheme 22). The latter then undergoes a ring-closing metathesis using Grubbs’ first-generation ruthenium catalyst to afford the desired natural product. O

B[(–)-Ipc]2 O Ph

OH

64 Et2O, –100°

H

Cl Et3N

Ph (72%) 92% ee

O O

O cat. (10 mol%)

O

CH2Cl2, 40°

Ph

Ph 181

PCy3 cat. = Ru Cl Cl Ph PCy3

Scheme 22

(76%) goniothalamin

ALLYLBORATION OF CARBONYL COMPOUNDS

B[(–)-Ipc]2 65,

1.

CH2Cl2

O (n-Bu)3Sn

63

H

2.

O

Br, KHMDS (n-Bu)3Sn

182 (92%) 98% ee

i-Pr N (CF3)2MeC(O) Mo (CF3)2MeC(O)

Pr-i Ph O

(–)-laulimalide

(n-Bu)3Sn (81%)

Scheme 23

A similar strategy has been employed in the synthesis of a dihydropyran required to achieve the synthesis of (−)-laulimalide (Scheme 23).205 Thus, allylation of the secondary alcohol resulting from a methallylation of 3-tri-nbutylstannylacrolein provided unsymmetrical ether 182, which is closed to a pyran with a ring-closing metathesis using Schrock’s molybdenum catalyst. The class of 3-silyl-substituted reagents provides, upon addition with aldehydes, allylic silanes that offer many options for further derivatization. Oxidative processes are described in previous sections (see the sections on Preparation of 1,2-Diols and 1,4-Diols). If the appropriate silicon substituents are chosen, formal [3+2] cycloadditions with aldehydes can be promoted under Lewis acid catalysis. For example, the mismatched addition of the Z-3-propyl3-benzhydryldimethyl allylsilane 183 to an α-benzyloxy aldehyde proceeds with low diastereofacial selectivity in favor of product 184; however, after protection of the secondary alcohol, an efficient [3+2] annulation provides the polysubsubstituted furan 185 in good yield and acceptable stereoselectivity (Scheme 24).206 The latter is brought forward to a tricyclic unit found in the antitumor natural product angelmicin B. A special α-substituted allylic boronate, reagent 187, has been developed as part of a tandem method for synthesizing trienes through an extended homologation of aldehydes.207 This process, a one-pot aldehyde allylation/ dioxene thermolysis, has been applied to a total synthesis of phenalamide A2 (Scheme 25).208 Thus, reagent 187 is added to unsaturated aldehyde 186 to give dioxene intermediate 188. Upon warming to 120◦ , 188 undergoes a formal retro[4+2] cycloaddition to give the desired dienal as a mixture of geometrical isomers. The addition of iodine promotes a complete Z- to E- isomerization to give the E,E-dienal intermediate 189. A dehydration of the latter then provides the tetraenal 190, an advanced intermediate subsequently transformed into phenalamide A2 .

64

ORGANIC REACTIONS

n-Pr

O

B[(+)-Ipc]2

THF

+

TBDMSO

(Ph2CH)Me2Si

H

–78° to rt

BnO

183

1. TBDMSOTf, Et3N (70%)

OH TBDMSO BnO n-Pr SiMe2(CHPh2) 184 (52%) 3:2 d.r.

2. BnOCH2CHO, SnCl4 (0.5 eq), 4 Å MS, CH2Cl2, –78°

O

Pr-n OH

(Ph2CH)Me2Si BnO TBDMSO

OBn

O Pr-n H

TBDMSO 185 (81%) 3.3:1 d.r.

OTIPS

H OBn

O

A-B subunit of angelmicin B

Scheme 24 O B

TBDMSO CHO +

Ph

O

rt, 2 d

O 186

1. 120°, 2 h

O O B O

toluene

O 187

TBDMSO

O

188

OH

Ph

(MeSO2)2O, (i-Pr)2EtN

O H

2. I2, rt, 0.5 h 3. H3O+

CH2Cl2, rt, 2 h

189 (69%)

TBDMSO

O

Ph

H 190 (85%)

OH

O

Ph

N H phenalamide A2

Scheme 25

OH

O

ALLYLBORATION OF CARBONYL COMPOUNDS

65

COMPARISON WITH OTHER METHODS

Despite the extensive efforts by numerous research groups over the course of more than two decades, there is still no carbonyl allylation methodology that possesses all of the following attributes: mildness and chemoselectivity, substrate generality (for both allylmetal reagent and aldehyde substrate), high levels of diastereo- and enantioselectivity, and high practicality (ease of use, low cost, non-toxicity, and low environmental impact). Very importantly, the ideal enantioselective allylation methodology would circumvent the use of a chiral auxiliary through a simple and efficient chiral catalyst.209 While several systems based on allylic boron reagents do possess many of the above attributes, several other allylation systems based on other metals (mainly tin, titanium, and silicon) demonstrate very interesting properties. It is noteworthy that a wide body of aldol-based reaction methods have been developed to afford chiral secondary alcohols, propionate units, and other useful intermediates closely related to those afforded by allylation processes. These methods are not described in this section but the interested reader will find several excellent reviews and monographs on the topic of aldol reactions.210 – 212 This section focuses on presenting a brief comparison of allylic boron reagents with other enantioselective allylation reagents. Methods Employing Allylic Tin Reagents Allylic trialkyltin reagents can react at high temperatures with aldehydes213 but because of the low acidity of the trialkyltin center, they are always employed as Type II allylation reagents that normally require activation of the carbonyl substrate with an external Lewis acid.15 This behavior contrasts the cyclic, organized transition structure of allylboration reactions. Consequently, additions of allylic tin reagents proceed through open transition structures that tend to demonstrate lower levels of diastereoselectivity (with 3-substituted reagents) compared with the corresponding boron reagents. Allylic trialkyltin reagents are highly nucleophilic in comparison to the corresponding trialkylsilanes. Their reactivity has contributed largely to their popularity. One major drawback of organotinbased reagents, however, is their high toxicity. Moreover, crotylation reagents are rather difficult to synthesize in geometrically pure form, albeit, this point is rather inconsequential because of the stereoconvergent (Type II) behavior of 3substituted tin-based reagents. Catalytic enantioselective methods that make use of achiral reagents constitute the most attractive carbonyl allylation processes. In this respect, the Keck allylation remains the most efficient and most popular system based on achiral allylic tin reagents (Eq. 107).214,215 This system has been employed mainly for simple allylations and methallylations of aldehydes. It makes use of a chiral BINOL-based titanium Lewis acid, which provides enantiomeric excesses as high as 94–96% for several types of aldehydes, both aliphatic and aromatic. The catalyst can be employed in a loading as low as 1 mol% when i-PrSSiMe3 is added.216 Efficient variants of these systems have been described for the allylation of ketones.217 A BINAP–AgOTf complex catalyzes the simple allylation of aldehydes with enantiomeric excesses as high as

66

ORGANIC REACTIONS

96% for benzaldehyde.218 Methallylations and crotylations of aldehydes under this catalytic system provide good enantioselectivities.219

O O RCHO

OPr-i

OPr-i (10 mol%)

SnBu 3

+

Ti

OH

4 Å MS, CH2Cl2, –20°

(Eq. 107)

R (78-98%) 89-96% ee

Additions of enantiomerically enriched allenyltin reagents provide homopropargylic alcohol products with high levels of stereoselectivity (Eq. 108).220 These reagents also function through Lewis acid catalysis. Although their preparation requires several steps through the intermediacy of enantiomerically pure propargylic alcohols, allenyltin reagents are effective with a wide range of aldehydes, including double diastereoselective additions with chiral α-substituted aldehydes.220 C7H15-n Me

OH

BF3•OEt2

+

RCHO

CH2Cl2

Sn(Bu-n)3

C7H15-n

R

(Eq. 108)

(>80%) up to 99:1 d.r.

Methods Employing Allylic Silicon Reagents Allylic trialkylsilicon reagents are less nucleophilic than the corresponding tin reagents. However, they are cheap and safer in terms of toxicity. One of the early successes in the area of catalytic enantioselective carbonyl allylation chemistry makes use of chiral acyloxy borane (CAB) catalysts and methallyltrimethylsilane (Eq. 109).221,222 This system works for aromatic, unsaturated, and aliphatic aldehydes but it gives the highest enantioselectivities in the reactions of 3-alkyl substituted reagents and aromatic aldehydes. Aliphatic aldehydes give noticeably lower selectivities, which probably accounts for the low level of adoption of this allylation method. i-PrO

O

CO2H O O

RCHO

+

O OPr-i O B Ar (10–20 mol%) TMS

EtCN, –78° Ar = 3,5-(CF3)2C6H3

OH

(Eq. 109)

R (55-99%) 54-88% ee

A method using dual activation has been developed in which a Lewis acid activates the aldehyde with concomitant nucleophilic activation of the allylic silicon reagent with fluoride anion. Thus, by using a BINOL-based titanium

ALLYLBORATION OF CARBONYL COMPOUNDS

67

tetrafluoride complex, both aromatic and aliphatic aldehydes can be reacted with allyltrimethylsilane with enantioselectivities up to 94% (Eq. 110).223 Aromatic aldehydes provide lower selectivity but this method is particularly efficient with hindered α,α-dialkylated aldehydes such as pivalaldehyde.224

TMS

+

RCHO

TiF4 (10 mol%), (S)-BINOL (10 mol%) CH2Cl2/CH3CN, 0°

OH

(Eq. 110)

R (69-93%) 60-94% ee

Allylic trialkoxysilanes are effective nucleophiles under the bifunctional Ag(I)–fluoride catalytic system when using a combination of KF and 18crown-6 as catalytic source of soluble fluoride anion (Eq. 111).225 Although this method requires the use of three molar equivalents of allyltrimethoxysilane, only 5 mol% of AgOTf with 2 mol% of BINAP are sufficient to afford enantiomeric excesses in the range of 93–97% for aromatic aldehydes. Aliphatic aldehydes display lower selectivities, and require a higher loading of the catalyst. The corresponding crotylation reactions are stereoconvergent, as both (E)- and (Z)crotyltrimethoxysilane provide the anti-propanoate product in 95% ee.225

Si(OMe)3

+

RCHO

(R)-BINAP (2 mol%), AgOTf (5 mol%), KF (5 mol%), 18-crown-6 (5 mol%) THF, –20°, 4 h

3 eq

OH R (61-95%) 87-97% ee

(Eq. 111) A similar Cu(I)-catalyzed reaction has been reported, and one example represents a modestly enantioselective addition to a ketone (Eq. 112).226

O Ph

+

Si(OMe)3

Me 1.5 eq

CuCl/(R)-tol-BINAP (15 mol%) TBAT (15 mol%) THF, rt

HO Ph (100%) 56% ee

(Eq. 112) Another approach toward activating allylic silanes exploits the ability of some basic solvents and additives to accelerate the additions of allylic halosilanes. In the latest advance, treatment of an allylic trichlorosilane with a dimeric chiral phosphoramide catalyst generates a highly reactive silane species which then allylates aldehydes to give homoallylic alcohols in high stereoselectivity (Eq. 113).227 Aromatic and unsaturated aldehydes react smoothly with the simple allyl reagent and both crotylsilanes to give homoallylic alcohols in good yields and high diastereo- and enantioselectivities.228 The mechanism of these allylations has been studied in detail. The high diastereoselectivity and the dependence of product stereochemistry on the geometry of γ-substituted silanes indicate that these allyltrichlorosilanes react like allylic boron reagents through the Type I pathway.

68

ORGANIC REACTIONS

A significant limitation to this approach is that it is not applicable to aliphatic aldehydes.

H H

R1CHO

R2

+

O N N O P P N N N 5 N Me Me

SiCl3

H H OH

(5 mol%) R1

CH2Cl2, –78°

R3 R2, R3 = H or Me

(Eq. 113)

R2 R3 (57-92%) 80-97% ee

Non-racemic α-substituted allylic silanes, in particular crotylsilanes, are very attractive reagents despite their rather tedious preparation. They were found to provide very high transfer of chirality in their additions to achiral aldehydes under Lewis acid catalysis (Eq. 114).229 These reagents have been tested several times in the context of natural product synthesis. Their diastereoselectivity (syn/anti) depends on several factors, including the nature of the aldehyde substrate, the reagent, and the nature of the Lewis acid employed. For example, the syn product can be obtained predominantly in the reaction of Eq. 114 by switching to the use of a monodentate Lewis acid such as BF3 . O BnO

+

CO2Me

H

SiMe2Ph

MgBr2

OH BnO

CO2Me

CH2Cl2, –25° anti (59%) 12:1 d.r.

(Eq. 114) Another approach for the activation of allylic silanes takes advantage of the fact that constraining silicon in a small ring increases its Lewis acidity. By reacting allyltrichlorosilane with 1,2-diols, diamines, or amino alcohols, allylchlorosilanes are generated in which the silicon is part of a strained heterocyclic 5membered ring. The most interesting aspect of this recent work comes from allylsilanes bearing chiral 1,2-amino alcohols and 1,2-diamines as substituents. The optimal reagents are derived from C2 -symmetrical cyclohexanediamines, and are exceptionally selective for a broad range of aldehydes, including unsaturated and aromatic ones (Eq. 115).230 These novel reagents are stable and easy to handle, and possess a long shelf-life. Interestingly, the corresponding crotylsilanes are also efficient reagents, and behave as Type I reagents by providing stereospecific crotylations of aldehydes.231 C6H4Br-4 Cl

N RCHO

+

Si N C6H4Br-4

OH

CH2Cl2 –10°, 20 h

R (61-93%) 95-98% ee

(Eq. 115)

ALLYLBORATION OF CARBONYL COMPOUNDS

69

Methods Employing Other Metals Several other metals have been examined in allyl transfer reactions to carbonyl compounds. Only modest success has been obtained except for a class of cyclopentadienyl titanium reagents based on a tartrate-derived auxiliary (Eq. 116).232 These reagents display a very high level of enantioselectivity in the simple allylation of several types of aldehydes, including hindered ones like pivalaldehyde (63% yield, 97% ee). A number of 3-substituted derivatives have been examined, including the E-crotyl reagent, which provides the anti propanoate products in excellent yields and over 98% ee for model aromatic and aliphatic aldehydes. These reagents are remarkably effective in double diastereoselective additions. Their inherent disadvantages are their preparation and their stoichiometric mode of stereochemical induction. Ti O

Ph Ph

O

O

Ph Ph O

OH

1. RCHO, –74° 2. NH4F

(Eq. 116)

R (86-93%) 94-97% ee

Allylic chromium species can also add to aldehydes. In this regard, an efficient catalytic enantioselective variant using allylic halides as substrates and manganese as co-oxidant has been described recently (Eq. 117).233 This method provides high enantiomeric excesses in the simple allylation of a wide range of aliphatic, aromatic, and heteroaromatic aldehydes. Crotylation examples are also very enantioselective, albeit with modest anti/syn diastereoselectivity.

N Cl Cr O O N

RCHO

+

Br

Bu-t Bu-t OH

(3 mol%) Mn, TESCl, DME/CH3CN (3:1), rt, 24 h

R (81-93%) 93-98% ee

(Eq. 117) EXPERIMENTAL CONDITIONS

Additions of allylic boron reagents are typically performed under experimentally simple conditions, and under a wide range of temperatures that is dictated by the reactivity of the particular reagent employed. Work-up conditions are discussed in a previous section. For the reaction itself, uncatalyzed additions can be performed in a wide variety of aprotic solvents. Non-coordinating solvents usually lead to shorter reactions times,21 but the identification of an optimal solvent in stereoselective additions is rather unpredictable and may require coordinating

70

ORGANIC REACTIONS

solvents for higher selectivity. The use of molecular sieves is strongly recommended when using water-sensitive allylic boronates. Lewis or Brønsted acid catalyzed additions are also better performed with non-coordinating solvents, typically toluene or methylene chloride. The literature describes only a few examples of allylations with a polymer-supported reagent,234 and with supported aldehydes.235,236

EXPERIMENTAL PROCEDURES MgBr

1. THF, 0° to rt

MeOB[(+)-Ipc]2

2. pentane

B[(+)-Ipc]2

(~100%)

(+)-B -Allyl bis(Isopinocampheyl)borane [General Procedure for Preparation of the Reagent Free of MgBr(OMe)].139 Allylmagnesium bromide in ether (48 mL, 1.0 M, 48 mmol) was added dropwise to a well-stirred solution of (+)-B-methoxy bis(isopinocampheyl)borane (15.8 g, 50 mmol) in THF (50 mL) at 0◦ . After completion of addition, the reaction mixture was vigorously stirred for 1 hour at room temperature, and the solvents were removed under vacuum (14 mm Hg, 2 hours). The residue was extracted with pentane (2 × 100 mL) under nitrogen, and stirring was discontinued to permit the MgBr(OMe) salt to settle. The clear supernatant pentane extract (free from the magnesium salts) was transferred to another flask using a double-ended needle through a Kramer filter. Evaporation of pentane (14 mm Hg, 1 hour; 2 mm Hg, 1 hour) afforded the pure title product in nearly quantitative yield. B[(+)-Ipc]2

+

O

1. ether, –100° H

2. NaOH, H2O2

OH (82%)

(R)-1,5-Hexadien-3-ol [Typical Procedure for the Simple Allylation of a Representative Aldehyde with the AllylB(Ipc)2 Reagent].139 Anhydrous ether (100 mL) was added to allylB[(+)-Ipc]2 , and the resulting solution was cooled to −100◦ . A solution of acrolein (2.8 g, 50 mmol) in Et2 O (50 mL), maintained at −78◦ , was slowly added along the side of the flask, kept at −100◦ . The reaction mixture was stirred for 0.5 hour at −100◦ , and MeOH (1 mL) was added. The reaction mixture was then brought to room temperature (1 hour) and treated with 3 N NaOH (20 mL) and 30% H2 O2 (40 mL). Heating the reaction mixture at reflux for 3 hours ensured the completion of the oxidation. The organic layer was separated, washed with water (30 mL) and brine (30 mL), dried over anhydrous MgSO4 , and filtered and concentrated under reduced pressure. Distillation afforded 4.17 g of the title product (82% yield), bp 54◦ at 20 mm Hg; 1 H NMR (300 MHz, CDCl3 ) δ 5.85 (m, 2H), 5.20 (m, 4H), 4.19 (m, 1H), 2.33 (m, 2H), 1.72 (br, 1H); 13 C NMR (300 MHz, CDCl3 ) δ 139.3, 133.4, 117.9, 115.2, 72.1, 41.0. GC analysis of its Mosher ester on a capillary Supelcowax column (15 m × 0.25 cm) showed the enantiomeric excess to be 96%.

ALLYLBORATION OF CARBONYL COMPOUNDS t-BuOK, n-BuLi, THF, –78°;

_

1. MeOB[(–)-Ipc]2, –78°

71

B[(–)-Ipc]2

2. BF3•OEt2, –78°

–45°, 10 min O 1.

OH

H , –78°, 3 h

(75%)

2. NaOH, H2O2

(2R,3R)-3-Methyl-4-penten-2-ol [Preparation of (−)-(Z )-Crotyl Bis(isopinocampheyl)borane and a Representative Reaction with Acetaldehyde].137 To a stirred mixture of t-BuOK (2.8 g, 25 mmol, dried at 80◦ /0.5 mm Hg for 8 hours), cis-2-butene (4.5 mL, 50 mmol), and THF (7 mL) at −78◦ was added n-BuLi (2.3 M in THF, 25 mmol). After complete addition of n-BuLi, the mixture was stirred at −45◦ for 10 minutes. The resulting solution was cooled to −78◦ , and methoxydiisopinocampheylborane in ether [1 M, 30 mmol, derived from (+)-α-pinene] was added dropwise. After the reaction mixture was stirred at −78◦ for 30 minutes, BF3 •OEt2 (4 mL, 33.5 mmol) was added dropwise. Acetaldehyde (2 mL, 35 mmol) was then added dropwise at −78◦ . The reaction solution was stirred at −78◦ for 3 hours and treated with 3 N NaOH (18.3 mL, 55 mmol) and 30% H2 O2 (7.5 mL). The resulting mixture was heated at reflux for 1 hour. The organic layer was separated, washed with water (30 mL) and brine (30 mL), dried over anhydrous MgSO4 , and filtered and concentrated under reduced pressure to afford the title product (75% yield, 90% ee, ≥99% d.r.), bp 78◦ /85 mm Hg; [α]23 D +19.40◦ (neat); 1 H NMR (CDCl3 ) δ 6.00–5.68 (m, 1H), 5.21–4.91 (m, 2H), 3.70 (p, J = 6 Hz, 1H), 2.25 (sextet, J = 7 Hz, 1H), 2.07 (s, br, 1H), 1.16 (d, J = 6 Hz, 3H), 1.04 (d, J = 7 Hz, 3H). 13 C NMR (CDCl3 , Me4 Si) δ 140.62, 115.06, 70.78, 44.87, 19.96, 14.85. t-BuOK, n-BuLi, THF, –78°;

1. MeOB[(–)-Ipc]2, –78° _

–45°, 10 min

2. BF3•OEt2, –78°

B[(–)-Ipc]2

O 1.

H , –78°, 4 h

2. NaOH, H2O2

OH (78%)

(2R,3S )-3-Methyl-4-penten-2-ol [Preparation of (−)-(E )-Crotyl Bis(isopinocampheyl)borane and a Representative Reaction with Acetaldehyde].137 To a stirred mixture of t-BuOK (2.8 g, 25 mmol, dried at 80◦ /0.5 mm for 8 h), trans-2-butene (4.5 mL, 50 mmol), and THF (7 mL) at −78◦ , was added n-BuLi (2.3 M in THF, 25 mmol). The mixture was stirred at −45◦ for 10 minutes. The resulting solution was recooled to −78◦ , and a solution of methoxydiisopinocampheylborane (1.0 M in ether, 30 mmol, derived from (+)-α-pinene) was added. After the reaction mixture was stirred at −78◦ for 30 minutes, BF3 •OEt2 (4 mL,

72

ORGANIC REACTIONS

33.5 mmol) was added dropwise. Acetaldehyde (35 mmol) was added dropwise at −78◦ . The reaction mixture was stirred at −78◦ for 4 hours and treated with 18.3 mL (55 mmol) of 3 N NaOH and 30% H2 O2 (7.5 mL). After the mixture was heated at reflux for 1 hour, the organic layer was separated, washed with water (30 mL) and brine (30 mL), dried over anhydrous MgSO4 , and filtered and concentrated under reduced pressure to afford the title product (78% yield, 90% ee, ≥99% d.r.); bp 78◦ /85 mm Hg; [α]23 D +9.141◦ (neat); 1 H NMR (CDCl3 ) δ 6.00–5.55 (m, 1 H), 5.30–4.95 (m, 2H), 3.4 (p, J = 7 Hz, 1H), 2.15 (sextet, J = 7 Hz, 1H), 1.70 (s, 1 H), 1.20 (d, J = 7 Hz, 3H), 1.05 (d, J = 7 Hz, 3H); 13 C NMR (CDCl3 , Me4 Si) δ 140.73, 115.76, 70.72, 45.64, 19.94, 15.72. O t-BuOK, n-BuLi THF, –78° to –50°

1. B(OPr-i)3, –78° _

2. (R,R)-DIPT

O B

O (>60%)

OPr-i OPr-i O

(R,R)-[(E )-2-Butenyl]diisopropyl Tartrate Boronate [Preparation of the (E )-Crotyl Diisopropyl Tartrate Boronate Reagent].37 An oven-dried 1-L three-neck round-bottom flask equipped with a magnetic stir bar and a −100◦ thermometer was charged with anhydrous THF (472 mL) and t-BuOK (48.0 g, 425 mmol). This mixture was flushed with Ar and cooled to −78◦ . trans-2Butene (42.0 mL, 450 mmol), condensed from a gas lecture bottle into a rubberstoppered 250-mL graduated cylinder immersed in a −78◦ dry ice–acetone bath, was added via cannula. n-BuLi (2.5 M in hexane, 170 mL, 425 mmol) was then added dropwise via cannula at a rate such that the internal temperature did not rise above −65◦ . After completion of the addition (roughly 2 hours on this scale), the cooling bath was removed and the reaction mixture was allowed to warm until the internal temperature reached −50◦ . The solution was maintained at −50◦ for exactly 15 minutes and then was immediately cooled to −78◦ . Triisopropylborate (80.0 g, 98.2 mL, 425 mmol) was added dropwise via cannula to the (E)-crotylpotassium solution at a rate such that the internal temperature did not rise above −65◦ . On this scale the addition time was approximately 2 hours. After the addition was complete, the reaction mixture was maintained at −78◦ for 10 minutes and then rapidly poured into a 2-L separatory funnel containing 800 mL of 1 N HCl saturated with NaCl. The aqueous layer was adjusted to pH 1 by using aqueous 1 N HCl, and a solution of (R,R)-diisopropyl tartrate (100 g, 425 mmol) in 150 mL of Et2 O was added. The phases were separated, and the aqueous layer was extracted with additional Et2 O (4 × 200 mL). The combined extracts were dried with anhydrous MgSO4 for at least 2 hours at room temperature and then vacuum filtered through a fritted glass funnel under a N2 blanket into an oven-dried round-bottom flask. The filtrate was

ALLYLBORATION OF CARBONYL COMPOUNDS

73

concentrated under reduced pressure to afford a colorless thick liquid, which was then pumped to constant weight (125 g) at 0.5–1.0 mm Hg. It was necessary for the neat reagent to be stirred to remove residual volatile materials, especially THF. Analysis of the crude product by capillary GC [50 m × 0.25 mm fused quartz SE-54 column (0.2 µm polydiphenylvinyl-dimethylsiloxane), 170◦ isotherm; tr of the E-isomer, 10.9 min vs. tr of the Z-isomer, 11.3 min; tr of butylboronate, 10.5 min] indicated that the isomeric purity of this batch of reagent was 99%; 12% of tartrate butylboronate was also present, reflecting incomplete metalation of (E)-2-butene in this experiment. The reagent is moisture sensitive, and it is better handled as a stable solution in toluene or THF. The (S,S)-reagent derived from (S,S)-DIPT had [α]23 D +36.5◦ (neat); 1 H NMR (300 MHz, CDCl3 ) δ 5.63–5.53 (m, 1H), 5.48–5.37 (m, 1H), 5.00–4.83 (m, 2H), 4.89 (s, 2H), 1.86 (br d, J = 6.4 Hz, 2H), 1.53 (br d, J = 6.3 Hz, 3H), 0.90 (d, J = 6.3 Hz, 12H); 13 C NMR (75.4 MHz, C6 D6 ) δ 169.0, 126.1, 125.3, 78.4, 69.6, 21.6, 18.1; 11 B NMR (115.8 MHz, C6 D6 ) δ 34.4; CIMS (NH3 ) (m/z): [M + 1]+ 299; HRMS (m/z): calcd for C14 H23 10 BO6 , 297.1617; found, 297.1618; HRMS (m/z): calcd for C14 H23 11 BO6 , 298.1581; found, 298.1683. O t-BuOK, n-BuLi THF, –78° to –25°

_

1. B(OPr-i)3, –78° 2. (R,R)-DIPT

O B

OPr-i OPr-i

O

O

(70-75%)

(R,R)-[(Z )-2-Butenyl]diisopropyl Tartrate Boronate [Preparation of the (Z )-Crotyl Diisopropyl Tartrate Boronate Reagent].37 The preparation of Z-crotylboronate from (Z)-2-butene is analogous to that described for the corresponding E-reagent with the following modification: on completion of the n-BuLi addition, the reaction mixture was warmed to −20◦ to −25◦ for 30–45 minutes before being cooled to −78◦ . This ensured near quantitative formation of the (Z)-crotylpotassium. Temperature control is less critical here since the (Z)-crotylpotassium species is highly favored at equilibrium (99 : 1). The remainder of this preparation was the same as that described above for the synthesis of the E-crotylboronate reagent. On a 100-mmol scale, the yield of Z-crotylboronate was 70–75% (1–2% of butylboronate) and the isomeric purity was >98% (generally >99%). The (R,R)-(Z)-reagent prepared from (R,R)-DIPT had [α]23 D −80.2◦ (c 2.42, CHCl3 ); IR (thin film) 3500 (br), 3220 (m), 2980 (s), 1745 (s), 1375 (s), 1220 (s), 1100 (s) cm−1 ; 1 H NMR (300 MHz, CDCl3 ) δ 5.76–5.67 (m, 1H), 5.55–5.48 (m, 1H), 5.05–4.99 (m, 2H), 4.92 (s, 2H), 1.91 (d, J = 7.8 Hz, 2H), 1.56 (d, J = 6.6 Hz, 3H), 0.94 (d, J = 6.3 Hz, 12H); 13 C NMR (75.4 MHz, C6 D6 ) δ 169.0, 124.6, 124.4, 78.4, 69.6, 21.3, 12.7; 11 B NMR (115.8 MHz, C6 D6 ) δ 34.8; CIMS (NH3 ) (m/z): [M+ ] 298; HRMS (m/z): calcd for C14 H23 11 BO6 , 298.1581; found, 298.1624.

74

ORGANIC REACTIONS O O B

OPr-i

O

OPr-i O

OH 4 Å MS H

(94%)

toluene, –78°

O

(1S ,2R)-1-Cyclohexyl-2-methyl-3-buten-1-ol [Representative Procedure for Additions of (E )-Crotyl Diisopropyl Tartrate Boronate to Aldehydes].37 A solution of (R,R)-isopropyl tartrate (E)-crotylboronate (3.19 g, 10.7 mmol, crude reagent, 99.3% isomeric purity) in 32 mL of dry toluene under N2 was ˚ molecular sieves (600 mg) and cooled to −78◦ . A treated with powdered 4 A solution of freshly distilled cyclohexanecarboxaldehyde (1.00 g, 8.92 mmol) in 10 mL of toluene was added dropwise over 30 minutes. The reaction mixture was stirred at −78◦ for 3 hours and then was treated with 10 mL of 2 N NaOH to hydrolyze the DIPT borate. The two-phase mixture was warmed to 0◦ and stirred for 20 minutes before being filtered through a pad of Celite. The aqueous layer was extracted with Et2 O (4 × 10 mL), and the combined organic extracts were dried over anhydrous K2 CO3 and filtered. Flash chromatographic purification on silica gel (60 × 150 mm column, 6 : 1 hexane/ether) provided 1.41 g of the title product (94% yield) in >99% d.r. (capillary GC analysis: Carbowax 20 column; 70◦ for 4 minutes then 10◦ /min to a final temperature of 150◦ ) and 86% ee as determined by chiral capillary GC analysis of the methyl ether. The product had [α]25 D −15.8◦ (c 1.02, CHCl3 , data obtained on a sample with >99% d.r. and 86% ee); 1 H NMR (300 MHz, CDCl3 ) δ 5.80 (ddd, J = 18.0, 10.9, 7.2 Hz, 1H), 5.15–5.10 (m, 2H), 3.11 (dd, J = 5.1, 5.1 Hz, 1H), 2.39 (m, 1H), 1.85–1.60 (m, 5H), 1.48–1.35 (m, 2H), 1.28–1.06 (m, 5H), 1.04 (d, J = 7.2 Hz, 3H); 13 C NMR (75.4 MHz, CDCl3 ) δ 140.4, 116.0, 78.8, 40.5, 40.3, 30.0, 27.0, 26.5, 26.4, 26.1, 17.0; Anal. Calcd for C11 H20 O: C, 78.52; H, 11.98. Found: C, 78.22; H, 12.20. O O B

OPr-i OPr-i

O

O

OH 4 Å MS H

(91%)

toluene, –78°

O

(1R,2R)-1-Cyclohexyl-2-methyl-3-buten-1-ol [Representative Procedure for Additions of (Z )-Crotyl Diisopropyl Tartrate Boronate to Aldehydes].37 The title product was prepared by the procedure described above using (R,R)isopropyl tartrate (Z)-crotylboronate (91% yield); [α]25 D +28.0◦ (c 0.61, CHCl3 , data obtained on a sample with >99% d.r.); 1 H NMR (400 MHz, CDCl3 ) δ 5.80 (ddd, J = 17.3, 10.0, 7.0 Hz, 1H), 5.08 (d, J = 17.3 Hz, 1H), 5.06 (d, J = 10.0 Hz, 1H), 3.18 (ddd, J = 5.0, 5.0, 4.3 Hz, 1H), 2.38 (m, 1H), 1.91 (d, J = 13.0 Hz, 1H), 1.73 (m, 2H), 1.64 (m, 1H), 1.58 (m, 1H), 1.41 (m, 1H), 1.35 (d, J = 4.3 Hz, 1H), 1.30–1.00 (m, 5H), 0.97 (d, J = 6.8 Hz, 3H); 13 C NMR (75.4 MHz, CDCl3 ) δ 142.0, 114.4, 78.6, 40.2, 39.8, 29.6, 27.8, 26.4, 26.2, 25.9, 13.1; MS (m/z): [M+ − crotyl] 113. Anal. Calcd for C11 H20 O: C, 78.51; H, 11.98. Found: C, 78.33; H, 12.03.

ALLYLBORATION OF CARBONYL COMPOUNDS

Ph

Ph

Ts

Ph

BBr3 CH2Cl2, 0°

Ts NH HN Ts

Br

75

N B

Sn(Bu-n)3 N

Ph

rt, 2 h

Ts Ph

Ts N B

N

OH

Ph

PhCHO

(91%)

CH2Cl2, –78°, 2.5 h

Ts

(R)-(+)-1-Phenyl-3-buten-1-ol [Preparation of (1R,2R)-N ,N
-Bis(p-Toluenesulfonamide)-1,2-diamino-1,2-diphenylethane Allyldiazaborolidine and a Representative Reaction with Benzaldehyde].50 (+)-(1R,2R)N ,N
-Bis(p-toluenesulfonamide)-1,2-diamino-1,2-diphenylethane (0.75 g, 1.44 mmol) was placed in a dry 25-mL round-bottom flask equipped with a magnetic stir bar and sealed with a septum. The flask was evacuated and flushed with argon three times. Freshly distilled CH2 Cl2 (12 mL) was added and the resulting solution was cooled to 0◦ , at which point BBr3 (1 M in CH2 Cl2 , 1.4 mL, 1.4 mmol) was added. The resulting solution was stirred at 0◦ for 10 minutes and then warmed to room temperature and stirred for 40 minutes. The solution was concentrated under vacuum (2 mm Hg) and rigorously protected from moisture. Freshly distilled CH2 Cl2 (5 mL) was added and removed under vacuum to give the bromoborane intermediate; 11 B NMR (96 MHz, CDCl3 ) δ 25.7; 1 H NMR (300 MHz, CDCl3 ) δ 7.32–7.28 (m, 6H), 7.26–7.22 (m, 4H), 7.20–7.09 (m, 4H), 7.02–6.98 (m, 4H), 5.11 (s, 2H), 2.33 (s, 6H). Freshly distilled CH2 Cl2 was added and the homogeneous solution was cooled to 0◦ and allyltri-n-butyltin (435 µL, 464 mg, 1.4 mmol) was added dropwise. The reaction mixture was stirred at 0◦ for 10 minutes, followed by 2 hours at room temperature. A purified aliquot displayed the following spectroscopic data: 1 H NMR (300 MHz, CDCl3 ) δ 7.52–6.92 (m, 18H), 6.21–6.09 (m, 1H), 5.34–5.11 (m, 2H), 4.78 (s, 2H), 2.77 (dd, J = 8.9, 1.9 Hz, 2H), 2.32 (s, 3H). The resulting solution was cooled to −78◦ and a solution of benzaldehyde (1.28 mL, 133.6 mg, 1.26 mmol) in CH2 Cl2 (1 mL) was added dropwise. The reaction mixture was stirred at −78◦ for 2.5 hours, and aqueous buffer (pH 7.5) was added. The aqueous layer was extracted with CH2 Cl2 (5 mL), the combined organic phases were washed with brine, and the solvent was evaporated. The residue was taken up in Et2 O/hexane (2 : 1, 10 mL), and the resulting solution was cooled to 0◦ for 20 minutes to complete precipitation of the solid. After removal of the (R,R)-bis(sulfonamide) (0.694 g, 92%) by filtration through a sintered glass funnel, the filtrate was vigorously stirred with aqueous KF (50%, 15 mL) at room temperature for 40 minutes. The organic layer was separated and dried with anhydrous MgSO4 , filtered, and the solvent was removed under reduced pressure. The product was purified by silica gel chromatography (hexane/Et2 O, 5 : 1) to afford 170 mg (1.12 mmol) of the title product (91% yield) as a colorless liquid; [α]D +44.78◦ (c 1.26, benzene); 1 H NMR (300 MHz, CDCl3 ) δ 7.41–7.28

76

ORGANIC REACTIONS

(m, 5H), 5.92–5.73 (m, 1H), 5.22–5.13 (m, 2H), 4.80–4.61 (m, 1H), 2.51–2.30 (m, 2H), 2.05 (d, J = 3.0 Hz, 1H). OH

Me3SiSiMe3

OTMS

110°, 12 h (99%)

1. Co(NO3)2 • 6H2O, pet. ether 2. SOCl2, rt, 4 h

1. HBCy2, DME, 0° to rt

OTMS

2. Me3NO 3. pinacol, 12 h

B (83%) O

O B

O

O

Cl (—)

(1R)-2-[1-Chloro-2-(E )-butenyl]pinacol Boronate [Preparation of a Chiral α-Chloro Allylic Boronate].83,237 (R)-3-Hydroxy-1-butyne (16.58 g, 236.5 mmol) and hexamethyldisilazane (19.09 g, 118 mmol) were heated to 110◦ for 12 hours. The mixture was then filtered through a short pad of silica gel to give 33.30 g (99%) of 3-trimethylsiloxy-1-butyne as an almost colorless liquid. Under an atmosphere of N2 , borane dimethylsulfide complex (8.4 mL, 84 mmol) was dissolved in DME (120 mL). The solution was cooled to 0◦ and cyclohexene (13.80 g, 168 mmol) was added. The mixture was stirred at 0◦ for 15 minutes and then warmed to room temperature and stirred for another 1 hour. The solution was cooled to 0◦ and 3-trimethylsiloxy-1-butyne (15.0 g, 84 mmol) was added. The reaction mixture was warmed to room temperature to dissolve the dicyclohexylborane, and stirred for an additional 1 hour. Anhydrous trimethylamine oxide (12.65 g, 84 mmol) was added in small portions to maintain the solution at reflux. The mixture was cooled to room temperature and stirred for an additional 1 hour. Pinacol (10.0 g, 84 mmol) was added and the mixture was stirred for 12 hours. The solution was filtered and the solvent was removed under reduced pressure. The resulting liquid was distilled (0.3 Torr) to give 18.60 g of pinacol (R)-(E)-2-(3-trimethylsiloxy-1-butene)boronate (83% yield), bp 68◦ /0.1 Torr; 1 H NMR (400 MHz, CDCl3 ) δ 6.58 (dd, J = 17.9, 4.3 Hz, 1H), 5.58 (dd, J = 17.9, 1.7 Hz, 2H), 4.30 (ddq, J = 6.5, 4.3, 1.7 Hz, 1H), 1.25 (s, 12H), 1.20 (d, J = 6.5 Hz, 3H), 0.09 (s, 9H); 13 C NMR (125 MHz, CDCl3 ) δ 156.5, 83.0, 69.6, 24.7, 23.5, 0.0. Anal. Calcd for C13 H27 BO3 Si: C, 57.78; H, 10.07. Found: C, 57.71; H, 10.16. The excess of trimethylamine was removed by washing the pinacol (R)(E)-2-(3-trimethylsiloxy-1-butene)boronate (5.0 g) in petroleum ether (50 mL) using 5% aqueous AcOH (10 mL), 4% aqueous NaHCO3 (10 mL), and saturated aqueous Na2 SO4 solution. The aqueous phases were back extracted each time with petroleum ether (10 mL). The combined organic layers were dried over anhydrous MgSO4 , filtered, and the solvent was removed under reduced pressure to afford pure pinacol (E)-2-(3-trimethylsiloxy-1-butene)boronate (4.84 g). Co(NO3 )2 •6H2 O (20 mg, 0.069 mmol) was added to a stirred solution of pinacol (R)-(E)-2-(3-trimethylsiloxy-1-butene)boronate (5.70 g, 21.1 mmol) in petroleum ether (130 mL). Freshly distilled SOCl2 (2.75 g, 23.1 mmol) was added, and

ALLYLBORATION OF CARBONYL COMPOUNDS

77

slow evolution of SO2 was observed. After 4 hours, when no more bubbling was observed, the mixture was filtered, and the solvent was removed under reduced pressure to afford 4.39 g of the crude title product (96% yield), which was distilled, bp 30◦ /0.1 Torr; 1 H NMR (400 MHz, CDCl3 ) δ 5.78 (ddq, J = 15.1, 6.4, 0.8 Hz, 1H), 5.65 (ddq, J = 15.1, 9.2, 1.5 Hz, 1H), 3.94 (d, J = 9.2 Hz, 1H), 1.71 (ddd, J = 6.4, 1.5, 0.8 Hz, 3H), 1.28 (s, 12H); 13 C NMR (125 MHz, CDCl3 ) δ 129.0, 128.1, 84.4, 24.4, 17.7. Anal. Calcd for C10 H18 BClO2 : C, 55.47; H, 8.38. Found: C, 55.50; H, 8.64. O B

OH

O + O

pet. ether H

(61%)

rt, 18 h

Cl

Cl

(1S ,2S )-(Z )-4-Chloro-2-methyl-1-phenylbut-3-en-1-ol [Representative Addition of Pinacol (1R)-2-[1-Chloro-2-(E )-butenyl]boronate to Aldehydes].67 To a solution of crude pinacol (1R)-2-[1-chloro-2-(E)-butenyl]boronate (1.80 g, 8.3 mmol) in petroleum ether (15 mL) was added benzaldehyde (0.59 g, 5.5 mmol) at 0◦ . After 18 hours at room temperature, the mixture was evaporated, the residue was dissolved in Et2 O, and triethanolamine (1.24 g, 1.10 mL, 8.3 mmol) was added under vigorous strirring. After 4 hours, the mixture was filtered and the solvent was removed by evaporation. The crude product was purified by flash column chromatography (7 : 3 petroleum ether/ether) to afford 0.66 g of the title product (61% yield); [α]20 D +44.5◦ (c 10, CDCl3 ); 1 H NMR (400 MHz, CDCl3 ) δ 7.34 (m, 5H), 6.13 (dd, J = 0.9, 7.2 Hz, 1H), 5.75 (dd, J = 7.2, 9.4 Hz, 1H), 4.50 (d, J = 7.3 Hz, 1H), 3.14 (dddq, J = 0.9, 6.9, 7.3, 9.4 Hz, 1H), 2.02 (br s, 1H), 0.90 (d, J = 6.9 Hz, 3H); 13 C NMR (100 MHz, CDCl3 ) δ 142.3, 133.6, 128.2, 127.7, 126.6, 119.2, 77.8, 39.8, 16.0. Anal. Calcd for C11 H13 ClO: C, 67.18; H, 6.66. Found: C, 67.27; H, 6.74. t-BuOK, n-BuLi THF, –78° to –50°

_

1. B(OPr-i)3, –78° 2. OH OH Ph

Ph O B

O H

(99%)

(1R,2S ,3R,4S )-2,3-O-[(E )-2-Butenylboryl]-2-phenyl-1,7,7-trimethylbornanediol [Preparation of the (E )-Crotyl Camphordiol Boronate Reagent].28 A 200-mL three-neck round-bottom flask equipped with a magnetic stir bar and a thermometer was charged with 110 mL of THF and t-BuOK (4.65 g, 41.5 mmol). The mixture was flushed with Ar and cooled to −78◦ . trans-2-Butene (2.46 g, 43.9 mmol), condensed into a rubber-stoppered 10-mL round-bottom flask kept at −78◦ , was added via cannula. n-BuLi (1.43 M in hexane, 29 mL, 41.5 mmol) was added dropwise over 1 hour with a syringe pump, so that the internal temperature did not rise at all. After completion of the addition, the reaction mixture

78

ORGANIC REACTIONS

was allowed to warm until the internal temperature reached −52◦ . The solution was maintained at −52◦ for 15 minutes, and then cooled back to −78◦ . Triisopropyl borate (10.53 mL, 45.6 mmol) was added dropwise over 30 minutes through a syringe pump. The reaction mixture was maintained at −78◦ for 2 hours, and was sealed under Ar and stored in a freezer for a few weeks without any noticeable change of its quality. The stored solution (10 mL) was reacted with 15 mL of aqueous 1 N HCl, and extracted with ether three times. The combined organic layers were mixed with (1R,2S,3R,4S)-2-phenyl-1,7,7trimethylbornanediol (220 mg, 0.89 mmol), stirred at ambient temperature for 45 minutes, and then concentrated under reduced pressure. Flash chromatography (5% EtOAc/hexanes, SiO2 pre-treated with 5% Et3 N/hexanes) yielded 277 mg of the title product as a colorless oil (99% yield); [α]25 D +10.5◦ (c 1.84, CHCl3 ); 1 H NMR (500 MHz, CDCl3 ) δ 7.42–7.41 (m, 2H), 7.34–7.24 (m, 3H), 5.43–5.30 (m, 2H), 4.71 (s, 1H), 2.13 (d, J = 5.5 Hz, 1H), 1.84–1.78 (m, 1H), 1.61–1.52 (m, 5H), 1.20–1.13 (m, 5H), 1.04–0.94 (m, 1H), 0.93 (s, 3H), 0.92 (s, 3H); 13 C NMR (125 MHz, CDCl3 ) δ 141.8, 127.4, 127.2, 126.7, 125.7, 125.2, 95.6, 88.5, 52.0, 50.2, 48.8, 29.6, 24.8, 23.6, 20.7, 18.0, 9.3; 11 B NMR (64 MHz, CDCl3 ) δ 34.2; HRMS-EI (m/z): calcd for C20 H27 O2 B, 310.21042; found, 310.20994. Anal. Calcd for C20 H27 O2 B: C, 77.43; H, 8.77. Found: C, 77.24; H, 8.86. O

Ph +

O B

O H

H n-C5H11

HO

Sc(OTf)3 (2 mol%) CH2Cl2, –78°

n-C5H11 (75%)

(3R,4R)-3-Methyl-1-undecen-5-yn-4-ol [Representative Procedure for Scandium-Catalyzed E-Crotylation of Aldehydes].28 Scandium trifluoromethanesulfonate (238 mg, 0.48 mmol) and CH2 Cl2 (5 mL) were introduced in a 50-mL round-bottom flask, and the mixture was cooled to −78◦ . 2-Octynal (1.03 mL, 7.25 mmol) was added, followed by a solution of (1R,2S,3R,4S)2,3-O-[(E)-2-butenylboryl]-2-phenyl-1,7,7-trimethylbornanediol (1.50 g, 4.83 mmol) in CH2 Cl2 (7 mL) dropwise over 30 minutes. The resulting mixture was stirred at −78◦ for 24 hours, then DIBAL-H (1.0 M in toluene, 14.5 mL, 14.5 mmol) was added. The mixture was stirred at −78◦ for 1 hour, then carefully poured into a 250-mL separatory funnel containing aqueous 1 N NaOH (50 mL). After the resulting layers were separated, the aqueous layer was extracted with EtOAc (3 × 25 mL). The combined organic layers were dried over anhydrous MgSO4 , filtered, and the solvent was removed under reduced pressure. Flash chromatography (5% EtOAc/hexanes) afforded 594 mg of the title product as a colorless oil (75% yield); [α]25 D +16.55◦ (c 2.00, CHCl3 ); 1 H NMR (500 MHz, CDCl3 ) δ 5.82 (ddd, J = 17.7, 10.4, 7.6 Hz, 1H), 5.17–5.12 (m, 2H), 4.19 (ddd, J = 6.2, 3.8, 1.9 Hz, 1H), 2.44–2.40 (m, 1H), 2.21 (ddd, J = 9.0, 7.1, 1.9 Hz, 2H), 1.82 (br s, 1H), 1.54–1.48 (m, 2H), 1.40–1.29 (m, 4H), 1.12 (d, J = 7.1 Hz, 3H), 0.90 (t, J = 7.1 Hz, 3H); 13 C NMR (125 MHz, CDCl3 ) δ 139.6, 116.4,

ALLYLBORATION OF CARBONYL COMPOUNDS

79

86.6, 79.5, 66.4, 44.7, 31.0, 28.3, 22.1, 18.6, 15.2, 13.9; HRMS-ES (m/z): calcd for C12 H20 ONa, 203.14064; found, 203.14084. 19 F NMR analysis of the Mosher ester derivative indicated 97% ee: (376 MHz, CDCl3 ) δ − 71.88 (major), −72.14 (minor). The fractions containing the diol auxiliary and those containing borate derivatives were concentrated, and treated with a solution of THF (2 mL), 1 N NaOH (1 mL), and H2 O2 (1 mL of a 30% aqueous solution) for 16 hours. The resulting mixture was diluted with water (5 mL) and extracted with EtOAc (3 × 10 mL). The combined organic layers were dried over anhydrous MgSO4 , filtered, and concentrated. Flash chromatography (5% EtOAc/hexanes) afforded 891 mg of recovered (1R,2S,3R,4S)-2-phenyl-1,7,7-trimethylbornanediol (75% yield). Ph t-BuOK, n-BuLi THF, –78° to –25°

_

1. B(OPr-i)3, –78°

O

2.

B

OH OH Ph

O H

(99%)

(1R,2S ,3R,4S )-2,3-O-[(Z )-2-Butenylboryl]-2-phenyl-1,7,7-trimethylbornanediol [Preparation of the (Z )-Crotyl Camphordiol Boronate Reagent].28 A 300-mL three-neck round-bottom flask equipped with a magnetic stir bar and a thermometer was charged with 110 mL of THF and t-BuOK (2.86 g, 25.5 mmol). After the mixture was flushed with Ar and cooled to −78◦ , cis-2-butene (1.50 g, 26.8 mmol), condensed into a rubber-stoppered 10-mL round-bottom flask kept at −78◦ , was added via cannula. n-BuLi (1.43 M in hexane, 17.9 mL, 25.5 mmol) was added dropwise over 1 hour such that the internal temperature did not rise above −70◦ . After completion of the addition, the cooling bath was removed and the reaction mixture was allowed to warm up until the internal temperature reached −25◦ . The solution was maintained at −25◦ for 30 minutes, and then cooled back to −78◦ . Triisopropyl borate (6.48 mL, 28.1 mmol) was added dropwise over 30 minutes. The reaction mixture was maintained at −78◦ for 2 hours, and was then rapidly poured into a 500-mL separatory funnel containing 200 mL of aqueous 1 N HCl. The layers were separated, and the aqueous layer was extracted with Et2 O (2 × 100 mL). The combined organic layers were dried over anhydrous MgSO4 , filtered, and concentrated on the rotary evaporator to a volume of about 60 mL. The resulting solution was approximately 0.4 M in (Z)-2-butenylboronic acid, and could be kept at 4◦ for a few weeks without any noticeable change in its concentration or its reactivity with diols. To this solution (3.00 mL, 1.20 mmol) was added (1R,2S,3R,4S)-2-phenyl-1,7,7trimethylbornanediol (246 mg, 1.00 mmol). The resulting mixture was stirred at ambient temperature for 30 minutes, and concentrated under reduced pressure. Flash chromatography (10% EtOAc/hexanes, SiO2 pre-treated with 5% Et3 N/hexanes) yielded 307 mg of the title product as a colorless oil (99% yield); [α]25 D +12.8◦ (c 1.73, CHCl3 ); 1 H NMR (300 MHz, CDCl3 ) δ 7.44–7.38 (m,

80

ORGANIC REACTIONS

2H), 7.35–7.22 (m, 3H), 5.52–5.34 (m, 2H), 4.70 (s, 1H), 2.13 (d, J = 5.2 Hz, 1H), 1.87–1.74 (m, 1H), 1.66–1.61 (m, 2H), 1.54–1.50 (m, 3H), 1.21 (s, 3H), 1.21–1.10 (m, 2H), 1.07–0.96 (m, 1H), 0.94 (s, 3H), 0.91 (s, 3H); 13 C NMR (125 MHz, CDCl3 ) δ 141.8, 127.4, 127.2, 126.7, 124.9, 123.5, 95.7, 88.6, 52.0, 50.2, 48.9, 29.6, 24.7, 23.6, 20.7, 12.5, 9.3; 11 B NMR (128 MHz, CDCl3 ) δ 34.1; HRMS-EI (m/z): calcd for C20 H27 O2 B, 310.21042; found, 310.21036. Anal. Calcd for C20 H27 O2 B: C, 77.43; H, 8.77. Found: C, 77.41; H, 8.77. Ph

O

O B

+ O H

HO

Sc(OTf)3 (2 mol%) H

CH2Cl2, –78°

n-C5H11

n-C5H11 (72%)

(3S , 4R)-3-Methyl-1-undecen-5-yn-4-ol [Representative Procedure for Scandium-Catalyzed Z-Crotylation of Aldehydes].28 The title compound was prepared in 72% yield by using a procedure analogous to that used to prepare (3R,4R)-3-methyl-1-undecen-5-yn-4-ol; [α]25 D +22.7◦ (c 1.27, CHCl3 ); 1 H NMR (300 MHz, CDCl3 ) δ 5.94–5.80 (m, 1H), 5.20–5.17 (m, 1H), 5.15–5.12 (m, 1H), 4.26 (ddd, J = 4.8, 2.0, 2.0 Hz, 1H), 2.50–2.38 (m, 1H), 2.22 (ddd, J = 6.9, 6.9, 2.0 Hz, 2H), 1.72 (br s, 1H), 1.57–1.46 (m, 2H), 1.44–1.26 (m, 4H), 1.11 (d, J = 6.9 Hz, 3H), 0.91 (t, J = 6.9 Hz, 3H); 13 C NMR (125 MHz, CDCl3 ) δ 139.2, 116.8, 86.7, 79.2, 66.3, 44.5, 31.0, 28.4, 22.1, 18.6, 15.6, 13.9; HRMS-EI (m/z): calcd for C12 H20 O, 180.15141; found, 180.15092. 19 F NMR analysis of the Mosher ester derivative indicated an optical purity of 95% ee: (376 MHz, CDCl3 ) δ –71.90 (major), −72.19 (minor). The fractions containing the diol auxiliary and the ones containing diol-borate derivatives were concentrated, and treated with a solution of THF (2 mL), 1 N NaOH (1 mL), and H2 O2 (1 mL of a 30% aqueous solution) for 16 hours. The resulting mixture was diluted with water (5 mL) and extracted with EtOAc (3 × 10 mL). The combined organic layers were dried over anhydrous MgSO4 , filtered, and concentrated. Flash chromatography (5% EtOAc/hexanes) afforded 891 mg of recovered (1R,2S,3R,4S)-2-phenyl-1,7,7-trimethylbornanediol (75% yield).

HO O B

O

+ O

Ph

H

OH SnCl4 (~10 mol%)

Na2CO3 (0.2 eq), 4 Å MS, CH2Cl2, –78°, 12 h

HO

(85%)

Ph

(3S )-1-Phenylhex-5-en-3-ol [Representative Allylation Catalyzed by a Chiral Diol-SnCl4 Complex].163 Into a flame-dried 25-mL round-bottom flask equipped with a rice needle stir bar were successively added (R,R)-1,2-dinaphthylethanediol (8.65 mg, 0.025 mmol, 0.11 eq), anhydrous Na2 CO3 (5.6 mg,

ALLYLBORATION OF CARBONYL COMPOUNDS

81

˚ molecular sieves (50 mg), and freshly dis0.05 mmol, 0.05 eq), activated 4 A tilled toluene (0.5 mL). To the stirred mixture under argon at room temperature was added 25 µL (0.025 mmol, 0.10 eq) of a 1.0 M solution of SnCl4 in CH2 Cl2 ; in order to obtain reproducible results, it is necessary to use a gas tight 25 µL syringe, and that all of the SnCl4 drops into the diol solution without touching the side walls. The resulting mixture was stirred for 5 minutes, cooled to −78◦ , and maintained at this temperature for 15 minutes, after which allyl boronic pinacol ester (46.2 mg, 1.1 eq) dissolved in 0.5 mL of toluene was added via syringe and this mixture was maintained at −78◦ for 15 minutes. Freshly distilled hydrocinnamaldehyde (32.6 µL, 0.25 mmol, 1.0 eq) was added and the reaction mixture was stirred at −78◦ for 12 hours. DIBAL-H in toluene (0.5 mL, 0.50 mmol, 2.0 eq) was added to reduce any remaining aldehyde. After 30 minutes, 2 mL of aqueous 1 N HCl was added, after which the reaction mixture was brought to room temperature and stirred for 1 hour. The dark brown biphasic mixture was extracted with Et2 O (2 × 25 mL) to give a clear etheral solution, which was washed with brine and dried over anydrous Na2 SO4 , filtered, and concentrated under reduced pressure. Purification of the residue by flash chromatography (5% EtOAc/hexanes) afforded 37.4 mg of the title product (85% yield, 78% ee); HPLC (chiracelOD, 5% i-PrOH/hexane, 0.5 mL/min, 254 nm) tr (major, 89%) = 26.19 min, tr (minor, 11%) = 37.62 min; [α]25 D −4.54◦ (c 0.41, CHCl3 ); IR (thin film) 3370, 1640 cm−1 ; 1 H NMR (300 MHz, CDCl3 ) δ 7.32–7.28 (m, 2H), 7.23–7.18 (m, 3H), 5.90–5.78 (m, 1H), 5.18 (m, 1H), 5.14 (m, 1H), 3.72–3.65 (m, 1H), 2.87–2.79 (m, 1H), 2.74–2.67 (m, 1H), 2.37–2.32 (m, 1H), 2.24–2.16 (m, 1H), 1.86–1.75 (m, 2H), 1.68–1.66 (s, 1H); 13 C NMR (125 MHz, CDCl3 ) δ 142.05, 134.6, 128.43, 128.38, 125.8, 118.3, 69.9, 42.1, 38.5, 32.05; HRMS-EI (m/z): calcd for C12 H16 O, 176.12011; found, 176.12011. Anal. Calcd for C12 H16 O: C, 81.77; H, 9.15. Found: C, 81.80; H, 9.14.

O

B

N

O Cr O Cl 88 (1 mol%)

O

+ O

OEt

B(pin) PhCHO O

(solvent)

Ph

45°

4 Å MS, rt, 1 h OEt

HO

H

O

OEt

(82%)

(R)-[(2R,6S )-6-Ethoxy-5,6-dihydro-2H -pyran-2-yl]phenylmethanol [Representative Example of a Tandem Catalytic Enantioselective [4+2] Cycloaddition/Allylboration].150 A mixture of 3-boronoacrolein pinacolate (364 mg, 2.00 mmol) and ethyl vinyl ether (1.90 mL, 20.0 mmol) was placed in an ovendried 10-mL round-bottom flask with a stir bar. To this solution was added the Jacobsen tridentate chromium(III) catalyst 88 (9.60 mg, 0.020 mmol) and powdered BaO (400 mg). After the mixture had been stirred for 1 hour at room

82

ORGANIC REACTIONS

temperature, benzaldehyde (424 mg, 4.00 mmol) was added. The reaction mixture was stirred at 40–45◦ for 24 hours, and diluted with EtOAc and filtered through Celite. The EtOAc solution was stirred for 30 minutes with an aqueous saturated solution of NaHCO3 . The organic layer was separated and the aqueous layer was extracted with EtOAc (2 × 20 mL). The combined organic layers were washed with an aqueous saturated solution of NaCl (20 mL), dried over anhydrous MgSO4 , filtered, and concentrated to afford the crude product. Purification by flash column chromatography (deactivated silica gel, 9 : 1 hexanes/Et2 O) afforded 384 mg of the pure title product as a clear oil (82% yield, 96% ee); HPLC (chiralpak AD-RH, 50% i-PrOH/H2 O, 0.300 mL/min, 210.8 nm) tr (major) = 8.60 min, tr (minor) = 10.64 min; [α]23 D +24.9◦ (c 1.0, CHCl3 ); IR (CH2 Cl2 , cast) 3451, 3035, 2877, 1640, 1257 cm−1 ; 1 H NMR (500 MHz, CDCl3 ) δ 7.40–7.26 (m, 5H), 5.79–5.75 (m, 1H), 5.40–5.36 (m, 1H), 4.78 (dd, J = 5.9, 5.9 Hz, 1H), 4.56 (dd, J = 7.4, 1.5 Hz, 1H), 4.32–4.28 (m, 1H), 3.96 (dq, J = 9.7, 7.1 Hz, 1H), 3.58 (dq, J = 9.7, 7.1 Hz, 1H), 3.11 (br s, 1H), 2.12–2.10 (m, 2H), 1.25 (t, J = 7.1 Hz, 3H); 13 C NMR (125 MHz, CDCl3 ) δ 139.8, 128.3, 128.0, 127.2, 125.4, 124.8, 98.5, 78.7, 76.8, 64.5, 31.1, 15.3; HRMS-ESI (m/z): [M + Na]+ calcd for C14 H18 O3 Na, 257.1154; found, 257.1152. TABULAR SURVEY

Within each table, entries are organized in the order of increasing number of carbons in the carbonyl substrate, not including protecting groups. This system was adopted so as to have similar substrates grouped together. The tables cover entries from the literature up until December 31, 2005. In each table, for the same aldehyde, allyl transfer reagents are grouped by the type of boron reagent involved; boranes are followed by boronates, and then the others such as borinates and borate salts. In all tables, entries with the same experimental conditions but differing only in the results (yield and selectivities) are listed under a single entry. In these instances, the results noted correspond to the best reported example. Table 1A contains entries of simple allyl (C3 H5 ) transfer to non-aromatic carbonyl substrates. Table 1B contains entries for aromatic and heteroaromatic substrates. Tables 2 and 3 cover entries of Z-crotylation and Ecrotylation respectively (cis and trans C4 H7 ). In the instances where a mixture of E/Z crotyl reagents is used, these entries are found in Table 2. It should be noted that readers interested specifically in the propionate products of crotylation reactions should also consult Table 4, which contains several entries of α-substituted crotylation reagents. Table 4 includes all entries with reagents having a substituent in the α position of the allylic group. Table 5 lists entries involving allyl transfer where the β position is substituted with a variety of functional groups. Table 6 reports entries where the γ position of the reagent is functionalized with a carbon or heteroatom-containing group. Table 7 presents examples of allenyl and propargyl group transfer. Table 8 consists of entries of cyclic allylic boron reagents, where the allylic unit is part of a ring. Table 9 contains entries of intramolecular allylboration reactions. For multiple substitution patterns, the

ALLYLBORATION OF CARBONYL COMPOUNDS

83

entries are ordered by least to most substituted; entries with the same number of substitutions are prioritized by α > γ > β. The authors would like to mention that some entries employing the Ipc reagents are inconsistent with respect to the nomenclature used for the absolute configuration of the reagent. These inconsistencies originate from the source references. The following abbreviations were used in the text and the Tables: Ac acac Adm AIBN Ald All B2 (cat)2 BBN BEC bmim Bn Boc BPS Bu Bz Cbz Conc. Cy dba DBU DDQ DEIPS DIPT DMB DMF DMPM DMSO dppe dppf d.r. ee emim equiv or eq. e.r. Et HQ 8-HQ

acetyl acetylacetone adamantyl 2,2
-azo(bis)isobutyronitrile aldehyde allyl bis(catecholato)diboron 9-borabicyclo[3.3.1]nonanyl 2-bromoethyloxycarbonyl butylmethylimidazolium benzyl tert-butoxycarbonyl tert-butyldiphenylsilyl butyl benzoyl carbobenzyloxy concentration cyclohexyl dibenzylideneacetone 1,8-diazabicyclo[5.4.0]undec-7-ene 2,3-dichloro-5,6-dicyano-1,4-benzoquinone diethylisopropylsilyl diisopropyl tartrate 3,4-dimethoxybenzyl dimethylformamide 3,4-dimethoxybenzyl dimethyl sulfoxide diphenylphosphinoethane diphenylphosphinoferrocene diastereomeric ratio enantiomeric excess ethylmethylimidazolium equivalent enantiomeric ratio ethyl hydroquinone 8-hydroquinoline

84

Icr IL Ipc Ket L.A. LDA MEM Mes min MOM MS Nph Ph Phth Piv PMB PMP Pr PTC pTSA pyr rt SEM siamyl TBAT TBDMS TBDPS TEAN TES Thex Tf TFA TfOH THF THP TIPS TMP TMS TMSE Tol Ts TPS Tr

ORGANIC REACTIONS

isocaranyl ionic liquid isopinocampheyl ketone Lewis acid lithium diisopropylamide 2-methoxyethoxymethyl mesityl minute methoxymethyl molecular sieves naphthyl phenyl phthalyl pivaloyl p-methoxybenzyl p-methoxyphenyl propyl phase-transfer catalyst p-toluenesulfonic acid pyridine room temperature 2-(trimethylsilyl)ethoxymethyl sec-isoamyl tetrabutylammonium triphenylsilyldifluorosilicate tert-butyldimethylsilyl tert-butyldiphenylsilyl tetraethylammonium nitrate triethylsilyl thexyl (2,3-dimethyl-2-butyl) trifluoromethanesulfonyl trifluoroacetic acid trifluoromethanesulfonic acid tetrahydrofuran tetrahydropyranyl triisopropylsilyl 2,2,6,6-tetramethylpiperidine trimethylsilyl 2-(trimethylsilyl)ethyl p-tolyl p-toluenesulfonyl triphenylsilyl trityl

85 P

P OR

CHMe 2

R=

BIPHEPHOS

Bu-t

OR

Bu-t

CHMe 2

MeO

MeO

(R)-Tol-BINAP

O P O

P(C 6H 4Me-4)2

OH

(R,R)-i-Pr-DUPHOS

Me 2CH

Me 2CH

(R)-BINOL

P(C 6H 4Me-4)2

OH

C HART 1. ACRONYMS FOR L IGANDS USED IN T ABLES

86

C2

O

H

Carbonyl Substrate

I (74), 93 I (—), >99

Ether, –78° to rt Ether, –100° a

"

I (—), 98 I (—), >99

THF, –78°, 3 h Ether, –100° a

"

I

(71), 96

–78°

(70), 94

(—), 98

–25°

B(2-d-Icr)2

OH

(—), 93

Pentane, ether, –100°

(—), 94

rt

(72), 7

(88)

0°

Temp

B[(+)-Ipc]2

B

I

Ether, –100° a

"

Ether, 3 h

I (—), >99

THF, –78°, 3 h

"

TMS

I (—), 98

Ether, –78° to rt

B(4-d-Icr)2 I (72), 99

I (—), 92

"

I THF, –78°, 3 h

B[(–)-Ipc]2

OH

OH

Product(s) and Yield(s) (%), % ee

Ether, –78° to rt

Neat, 0-10°

Conditions

B[(–)-limonene]

BEt2

Allylborane Reagent

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS A. NON-AROMATIC CARBONYL SUBSTRATES

139, 242

240

204

143

139

240

239, 136a

139, 241

240, 136a

240

136, 239,

239, 136a

238

Refs.

87 B

B

MeO

B

"

B

O

O

O

N

O

N

O

O

SO2Me

Ph

Ph

O

Ph

Ether, –78° to rt, 2 h

Hexane, –40°

Hexane, –40°

rt, 12 h

Hexane, –40°, 1 h;

Hexane, –40° I

I

I (47), 96

OH

I (82), 33

I (92), 65

OH

I (67), 34

B[(+)-longifolene]2

O

I (72), 93

B[(+)-10-methyl-Ipc]2 Ether, –78° to rt

Ether, –78° to rt

I (65), 11

Ether, –78° to rt

B[(+)-β-pinene]2

(92), 38

(86), 86

133

122

122

244

122, 243

239, 136a

239, 136a

239, 136a

88

C2

CF3

O

O

O

R

H

H

Carbonyl Substrate

B

B(2-d-Icr)2

B[(+)-Ipc]2

BBN

B[(–)-Ipc]2

O

N

O S O

Allylborane Reagent

Pentane, ether, –100°

Pentane, ether, –100°

Pentane, rt, 2 h

Pentane, ether, –100°

Ether, –78°, 7 h

Conditions

I I (—), >99

CF3

OH

OH

OH

OH

2

(84)

NMe2 OBBN

(50), 99

(90) (50-57)

OEt

(95)

(95) OAc

Cl

R

(71), 94

(51), 92

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

248

248, 249

103

247

245, 246

Refs.

89

RO

R = TBDMS

R = Bn

R = Bn, TBDMS, TBDPS

R = Bn, TBDPS

R = PMB

H R = Bn

O

O

B

O

B

O

O

O

O

O

Ph

O B O

B

O

O

N Bn

O

OPr-i

OPr-i

O

N

Bn

O

OPr-i

OPr-i

B(2-d-Icr)2

B[(+)-Ipc]2

Pentane, ether, –100°,

B[(–)-Ipc]2

4 Å MS, toluene, –78°

46 h

4 Å MS, toluene, –78°,

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

4 Å MS, toluene, –78°

Ether, –78°, 4 h

12 h

Ether, –78° to rt,

1h

—

B[(–)-Ipc]2

OH

I

OH

I

OH

TBDPS

TBDMS

Bn

(45), 86

(61), 90

(76), 90

(62), 77

(42-70), 56

R

(42-70), 59

TBDPS

(95), 71

(—)

Bn

R

I (42-70), 59

RO

I

I

I (75), 94

RO

I (74), 92

RO

170

131

27, 28

170

253

252

251

250

90

C2

O

O

O

O

MeO

Br

H H

O

O

OH

H

O

OEt

OBu-n

O

H

Carbonyl Substrate

3

3

B

B

B[(–)-Ipc]2

B(4-d-Icr)2

B[(+)-Ipc]2

2

BC6H13

B(Bu-n)2

B[(+)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

Ether, –100°, 1 h

15 min

Ether, –110° to 20°,

15 min

Ether, –110° to 20°,

Neat, 0-20°

Neat, 0°

Neat, 0°

Neat, 0°

THF, –100°, 4 h

THF, –100°, 4 h

Conditions

MeO

Br

Br

I (80)

I (70)

I (88)

I

OH

O

OH

OH

OH

OH

2

OH

OH

OH

(82), 94

(50), 92

(50), 89

(85)

(82), >98, 97:3 d.r.

(80), >98, 97:3 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

257

256

256

238

238

238

238

254

254, 255

Refs.

91

C3

I

O

O

H

O

H

H

B

TMS

O Ph

B[(–)-Ipc]2

B[(+)-Ipc]2

O

Ether, –78°

Ether, –90°

Hexane, –40°

I

I

OH

I

OH

OH

I (71), >99

I (—), >99

(49), 90

(49), 95

(86), 50

Ether, –100° a

"

B

THF, –78°, 3 h

B(2-d-Icr)2

Ether, –78°, 3 h

I (—), 98

Ether, –100° a

" OH

240

I (—), 93

THF, –78°, 3 h

259

258

122

143

139

240

139

239, 136a

I (79), 86

Ether, –78° to rt

139

240

B(4-d-Icr)2

(—), 95

(—), 92

"

I (—), 96

I

OH

Ether, –100° a

THF, –78°, 3 h

"

B[(–)-Ipc]2

92

C3

TMS

O H

O H

Carbonyl Substrate

TMS

B

I (76), 91 I (—), 91

Ether, –78° to rt THF, –78°, 3 h

THF, –78°, 3 h

B(4-d-Icr)2 "

B(2-d-Icr)2

OH

240

240

240

239, 136a

136, 136a I (—), 86

141

I (71), 86

(—), 94

(80), 96

238

238

262, 1

261

Ether, –78°, 3 h

I

OH

I (90)

(71)

(48), 98

Refs.

THF, –78° to rt

Ether, –100°, 3 h

Neat, 0-10°

I (92)

I

OH

OH

Product(s) and Yield(s) (%), % ee

"

Pr-n

Neat, 0-10°

–70° to 130°

Ether, –100°, 1 h

Conditions

B[(–)-Ipc]2

B

B

B(Bu-n)2

3

B[(+)-Ipc]2

Allylborane Reagent

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

93

O

O

O

N

B

O

BBN

B

BEt2

B

O

B

O

Ph

Pr-n

Ph

O

SO2Me

N

O

O

MeO

B

B

Neat, 80-100°

Pentane, rt, 2 h

Neat, 0-10°

Neat, 0-10°

Neat, 80-100°

Ether, –78° to rt, 2 h

Hexane, –40°

Hexane, –78°

O

I (99)

I (92)

I

B

O

OH

O

OH

B

O

I (85), 44

I

OH

(96)

(91)

(85)

(92), 92

(91), 77

263

103

238

238

263

133

122

122, 244

94

C3

RO

CF3

C 2F 5

CF3

O

R = TBDMS

H

SiMe2Ph

CF3

H

R = Bn

O

O

O

O

Carbonyl Substrate

TMS

Ether, –78°, 4 h Ether, –100° to –78°

Ether, –100°, 3 h

Ether, –78° to rt, 3 h

Neat, 0-10°

"

Pr-n

Neat, 0-10°

Pentane, ether, –100°

Pentane, ether, –100°

Neat, 80-100°

Conditions

B[(–)-Ipc]2

B

B[(+)-Ipc]2

B

BEt2

B(2-d-Icr)2

B[(+)-Ipc]2

B

O

Allylborane Reagent

I

OH

O

I

265

141

264

(92), 84

111

238

238

248

248

263

I (82), 85

I

(66), 6

(78)

(65), >99

(70)

Refs.

I (90), 85

RO

OH

HO SiMe2Ph

I (83)

CF3

CF3 OH

I (—), >99

C2F5

CF3

B

O

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

95

Ether, –78° to rt,

THF, –78°, 3 h

Toluene, –78° Ether, THF

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

" B(2-d-Icr)2

R = PMB

R = Bn

R = TBDPS

R = TBDPS

R = TBDMS

R = Bn, TBDPS

R = PMB

R = Bn

O

O

O

Ph

O B O

B

O

B

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B(2-d-Icr)2

"

Ether, –78°

"

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Ether, –78°

3h

Ether, –78° to rt,

4h

THF, –78°

B[(–)-Ipc]2

R = TBDPS

RO

RO

I

OH

(—), 63

OH

OH

(—), 66 TBDPS

I

Bn

R

I (96)

I (87), >95

I (98), 84

RO

I (83), 94

(90), 94

(86), 93

(—), 66

27, 28

170

170

273

272

271

264

269, 270

253, 268

267

I (97), 91 I (90), 85

266

I (99), 88

96

C3

O H

Boc

H

B

O

B

O

"

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

–78°, 4 h

4 Å MS, toluene,

–78°, 4 h

4 Å MS, toluene,

THF, –78° to rt, 12 h

— O

O B

R = Bn

Ether, –78°, 3 h

Ether, –78°, 3 h

—

Conditions

Ether, –78°, 3 h

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

B[(+)-Ipc]2

Carbonyl Substrate

R = TBDMS

OR R = Bn

HN

O

OH

OH

Boc

I

OR

OR

OH

OH

I (97), 65:35 d.r.

I (—), 55:45 d.r.

I (82), 92:8 d.r.

OR

OR

HN

OH

(16), 84:16 d.r.

(—), 72:28 d.r.

(75), 96:4 d.r.

(80), 94:6 d.r.

(75), 97:3 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

170

170

275

118

167, 166

167, 166

167, 166

274

Refs.

97

H

O

O

N

N

O

O N

OH

Boc

O

B

O

"

B

O

O

O

O

O OPr-i

O

OEt

OEt

O

OPr-i

Toluene

Toluene, –78°, 3 h

4 Å MS, –78°

CH2Cl2, rt

O B

—

"

Boc

I

N

N

Boc

OH

Boc

I

I (77), 89:11 d.r.

I (84), 83:17 d.r.

O

O

OH

I (80), 96:4 d.r.

N

OH Ether

Ether

I

I (95), 70:30 d.r.

OTBDMS

OH

O B[(+)-Ipc]2

B[(–)-Ipc]2

CH2Cl2/H2O, rt, 30 min

n-Bu4NI (10 mol%),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (0.05 mol%),

Boc

H

H

"

BF3–K+

Boc

O

OTBDMS

O

ether

(—)

(—)

85:15

85:15

toluene THF

d.r. 89:11

Solvent (77)

(—), 66:34 d.r.

(—), 88:12 d.r.

(52), 97:3 d.r.

(69), 70:30 d.r.

278

282

277

277

279, 280

277, 278

281

276

99

98

C3

N

N

N

Boc

O

Et

O

Boc

TBDPSO

O

O

O

O

O

O H NHBoc

H

H

H

Carbonyl Substrate

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B

O

O

O

OEt

OEt

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

"

B

O

O

Allylborane Reagent

Ether, –78°, 3.5 h

Toluene, –78°, 3 h

Toluene, –78°, 3 h

THF, –78° to rt

Ether

Toluene, –78°, 3 h

4 Å MS, –78°

Conditions

N Boc

I

N

N

N

Boc

OH

Boc

OH

Et

TBDPSO

O

O

O

O

OH

OH

NHBoc

I (84), 90:12 d.r.

I (78), 82:18 d.r.

O

OH

(84)

(89)

(75)

Et2O

THF (84)

(—)

(—)

d.r.

90:10

87:13

85:15

(68), 12:1 d.r.

toluene

Solvent

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

285

282

282

283, 284

278

282

277

Refs.

99

O

HO

HO2C

TPSO

O

O

O

H

O H

NHBoc

O

B

TMS

O

"

24-48 h

Toluene, –78°,

24-48 h

CH2Cl2, –78°,

–78° to rt, 13 h

"

Petroleum ether,

O

Ether, –78°

Ether, –78°

Ether, –100°, 6 h

–10° to rt, 15 h

Et3N, CH2Cl2,

–10° to rt, 13 h

Et3N, CH2Cl2,

Ether, –78°, 3.5 h

B

B

TMS

B[(+)-Ipc]2

B(OPr-i)2

B(OPr-i)2

B[(–)-Ipc]2

O

HO

OH

I

NHBoc

O

I (—), 71:29 d.r.

I (75), 80:20 d.r.

I (60), 78:22 d.r.

O

OH

I (—), 95:5 d.r.

O

HO

HO2C

HO

TPSO

OH

(—), >99:1 d.r.

(88), 97:3 d.r.

(84)

(86)

(—), 12:1 d.r.

124

124

288

143

143

287

109

105

286

100

C3

O

O

O H

Carbonyl Substrate

B

O

B

O

"

B

O

B

O

O

O

O

O

O

O

OPr-i

OPr-i

Allylborane Reagent

4 Å MS, toluene

24-48 h

CH2Cl2, –78°,

24-48 h

Toluene, –78°,

24-48 h

CH2Cl2, –78°,

See table

Conditions

O

O O

OH

I

I (—), 68:32 d.r.

I (—), 76:24 d.r.

(—)

d.r.

77:23 93:7

–78°

70:30

64:36 –23°

0°

rt

Temp

58:42

77:23 71:29

79:21 rt

ether

0° to rt

75:25 rt

hexane

DMF

73:27

–78°

hexane

rt

71:29

rt

toluene

THF

77:23

rt –78°

toluene

–78°

CH2Cl2

d.r. 80:20

Temp

CH2Cl2

(—) Solvent

I

I (—), 81:19 d.r.

O

OH

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

125

124

124

124

118

Refs.

101 N

"

B

O

B

O

O

O

O

OPr-i

OPr-i

O

N

Toluene, –78°, 24-48 h

CH2Cl2, –78°, 24-48 h

CF3 4 Å MS, toluene, –78°, 8h

Toluene, –78°, 24-48 h

"

O

CH2Cl2, –78°, 24-48 h

"

CF3

4 Å MS, toluene, –78°

"

O

I (—)

4 Å MS

"

–78° –30° –23° –78° –78° –78° –63°

CH3CN CCl4 THF CH2Cl2 ether CHCl3

O

I

I (86), 93:7 d.r.

O

OH

I (86), 95:5 d.r.

I (79-83), 92:8 d.r.

I (—), 61:39 d.r.

(91), 96:4 d.r.

Temp

toluene

89:11

1 Solvent

93:7

0.2

d.r. 94:6

x 0.1

I (—), 93:7 d.r.

I (—)

4 Å MS, toluene, –78°

" xM

d.r.

25:75

64:36

61:39

70:30

71:29

72:28

97:3

124

124

132

124

124

170

125

125

102

C3

O

O

O H

Carbonyl Substrate

O

B

O

B

O

B

O

"

B

O

O

O

O

O

O

O

O

N

Bn N

n

Bn

CF3

N O

N

O

OPr-i

OPr-i

Allylborane Reagent

CH2Cl2, H2O, rt, 5 h

43 h

4 Å MS, toluene, –78°,

CF3 4 Å MS, toluene, –78°, 8h

4 Å MS, toluene

4 Å MS, –78°

Conditions

O

93:7 94:6 96:4 98:2

0° –23° –78°

81 84

R,R S,S

Reagent % Conv.

I (81), 67:33 d.r.

I

d.r.

d.r.

CH2Cl2

toluene

Solvent

2:98

99.7:0.3

(—)

rt

Temp

I

I (73), >99:1 d.r.

I (—)

O

OH

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

d.r. 96:4

98:2

234

131

132

125

125, 170

Refs.

103

C4

O

O

O

H

O H

TMS

O

B

O

B

O

B

O

O

O Ph

Cy

N O

N

Ph

B(2-d-Icr)2

B

BBN

O

O

O

0.5 M

B

O

B

n

Cy

Neat, 80-100°

CH2Cl2, H2O, rt, 3 h

Hexane, –40°

Ether, –100° a

Ether, –100°, 3 h

Pentane, rt, 2 h

36 h

4 Å MS, toluene, –78°,

t-BuCHO (0.1 equiv),

–78° to rt, 13 h

Petroleum ether,

O

O

OH

OH

OH

OH

OH

O

B

O

OH

I (87), 96:4 d.r.

(87)

(70)

(84), 30

(—), >99

(85), 97

(91)

(53), >99:1 d.r.

263

234

122

241

141

103

132

288

104

C4

n-Pr

O

O

O

H

Carbonyl Substrate

Ph B

THF, –78° to rt

B[(–)-Ipc]2

THF, –78° to rt

"

B

Ether, –78°, 3 h

Ether, –78° to rt

"

TMS

Ether, –100° a

Neat, 0-10°

B[(–)-Ipc]2

BEt2

Pentane, rt, 2 h

BBN

Ether, –78°

Neat, 0-10°

THF, –78° to rt

Conditions

BEt2

B[(–)-Ipc]2

Allylborane Reagent

I

OH

I

OH

I (79), >99

I (88), 83

I (72), 87

n-Pr

n-Pr

OH

I (77), 81

I (94)

I

OH

OH

(—), 96

(89)

(79), 35

(77)

(76), 79

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

143

166

240

136, 136a

139, 289

238

145

136a

103

238

136a

Refs.

105 "

B

B

B

O

O

O

O

N

O

O

Ph

SO2Me

O

NHBn

NHBn

rt, 12 h

Hexane, –40°, 1 h;

Hexane, –40°

Ether, –78° to rt, 2 h

Toluene, –78°, 18 h

—

B(OBu-n)2

I

OH

I I (93), 72

n-Pr

OH

I (78), 96

n-Pr

n-Pr

OB(OBu-n)2

I (—), 94

(93), 72

(—), 95

(50-60)

THF, –78°, 3 h

"

I

(—), >99

Ether, –100° a

B(2-d-Icr)2 n-Pr

I (—), 88

THF, –78°, 3 h

"

OH

239, 166,

I (73), 89

Ether, –78° to rt

"

244

122

133

290

2

240

242

139, 241,

240

240

139

I (—), 98

Ether, –100° a

B(4-d-Icr)2

106

C4

i-Pr

O

O

H

Carbonyl Substrate

B

t-Bu

i-Pr

TMS

TMS

Ph

240

I (—), 88 I (—), 96

Ether, –100° a

"

139

136, 136a

I (86), 90

141

141

141

141

263

145

Ether, –78°, 3 h

I (95), 72

I (87), 24

(85), 96

(86)

(80), 87

Refs.

Ether, –78° to rt

Ether, –100°, 3 h

Ether, –100°, 3 h

I

I (82), 71

i-Pr

O B

OH

O

HO

Product(s) and Yield(s) (%), % ee

"

TMS

Ether, –100°, 3 h

Ether, –100°, 3 h

Neat, 80-100°

Ether, –78°

Conditions

B[(–)-Ipc]2

B

B

B

B

B

O

Allylborane Reagent

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

107

C 3F 7

O

O

SiMe2Ph

H

B

TMS

O N SO2Me

Ph

B[(+)-Ipc]2

B(2-d-Icr)2

B[(+)-Ipc]2

B

B

O

THF, –78°, 3 h

"

O

Ether, –100° a

B(2-d-Icr)2

Ether, –78° to rt, 3 h

Pentane, ether, –100°

Pentane, ether, –100°

Ether, –78° to rt, 2 h

Hexane, –40°

Ether, –78°, 3 h

I (—), 98

Ether, –100° a

"

OH

OH

OH

I

I

HO SiMe2Ph

I (—), >99

C3F7

i-Pr

i-Pr

i-Pr

OH

I (—), 94

i-Pr

I (—), 95

THF, –78°, 3 h

OH

I (73), 97

Ether, –78° to rt

B(4-d-Icr)2 "

(65)

(55), 99

(51), 94

(88), 70

(70), >99

(—), >99

111

248

248

133

122, 244

143

240

139

139, 241

240

239, 136a

108

C4

RO

N H

O

B

B

O

O

3

R = TBDPS

H

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

O

B[(–)-Ipc]2

BEt2

B(OPr-i)2

Allylborane Reagent

H R = TBDMS, TBDPS, Bn

O

H

Et

O

TBDMSO

I

Cl

HO2C

O

Carbonyl Substrate

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

THF, reflux, 2 h

3h

Ether, –100° to –78°,

Ether, –100°, 0.5 h

Neat, 0-10°

–10° to rt, 13 h

Et3N, CH2Cl2,

Conditions Et

I (—), 82

RO

N H

I

OH

OH

(90)

OH

OH

TBDMSO

I

Cl

HO2C

OH

(91)

(73)

(90)

Bn

TBDPS

TBDMS

R

(—), 78

(—), 74

(—), 77

(68), 91

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

131

170

293, 294

292

291

238

105

Refs.

109

RO

H

R = TBDPS

R = Bn

R = PMB

O

O

O

CF3

N

Ether, –78°, 3 h

Ether, –78°, 3 h

—

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

Ether, –110°, 3 h a

5h

4 Å MS, THF, –78°,

t-BuCHO (0.1 equiv),

36 h

4 Å MS, toluene, –78°,

t-BuCHO (0.1 equiv),

Ether, –100°

CF3

Cy

37 h

4 Å MS, toluene, –78°,

"

O

N

Bn

Cy

N O

N

O

N

Bn N

B[(–)-Ipc]2

B O 0.5 M

O

O

B O 0.5 M

O

B

O

O

I

OH

RO

RO

OH

OH

I (80), 96:4 d.r.

I (70)

RO

I (80), 95

I (72), 94

I (58), 94

(76), 99:1 d.r.

(78), 98:2 d.r.

(92)

280

167

167

296

295

132

132

131

110

C4

RO

H

R = TBDMS

R = TBDPS, TBDMS

R = TBDPS

R = TBDMS, TBDPS, Bn

O

Carbonyl Substrate

B

O

B

O

0.5 M

B

O

B

O

B

O

O

O

O

O

O

O

O

O

O

CF3

N O

N

CF3

N O

N

Cy

N O

N

O

OPr-i

OPr-i

Allylborane Reagent

CF3 4 Å MS, THF, –78°, 9h

CF3 4 Å MS, THF, –78°

Cy 4 Å MS, THF, –78°, 36 h

4 Å MS, toluene, –78°

Toluene, rt

Conditions

RO

I

54:46

(76), 94:6 d.r.

95:5

(72) 9h TBDMS

OH

92:8

(82)

d.r.

54:46

Bn

8h

Time

83:17

d.r.

Refs.

132

132

132

170

169, 297,

52:48 169

TBDPS

TBDMS

R

TBDPS

R

(—)

79:21

(—)

TBDPS Bn

d.r. 89:11

(71)

TBDMS

(—)

R

I

I (71), 95:5 d.r.

I

RO

OH

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

111

RO

H

R = TBDMS, TBDPS, Bn

R = Bn

O

R = TBDPS

R = TBDMS, TBDPS, Bn

O

O

O

B

O O

O N O

N

Bn

B[(+)-Ipc]2

Bn

CF3

N O

N

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

O

CF3

4 Å MS, toluene

Ether, –78°, 3 h

Ether, –78°, 3 h

8h

4 Å MS, THF, –78°,

4 Å MS, toluene, –78° I

OH

OH

(76) (43) (48) (35) (68) (56) (53)

37 h 21 h 36 h 44 h 25 h 21 h 23 h 23 h

–78° –50° –78° –78° –78° –50° –50° –50°

TBDMS TBDMS TBDPS TBDPS TBDPS Bn Bn

S,S R,R S,S R,R R,R S,S R,R

7:93

93:7

5:95

3:97

95:5

3:97

95:5

d.r. 97:3 (46)

Time Temp TBDMS

(—), 95:5 d.r.

(—), 98:2 d.r.

80:20

131

167

167

132

87:13 170

(—)

(72)

Bn

TBDPS

d.r. 81:19 169, 297,

(—)

TBDMS

R

S,S

Reagent R

RO

RO

RO

OH

I (83), 97:3 d.r.

RO

OH

112

C4

Br

O

H

OH

O

O

H

R = TBDMS

O

H

MeO B

O

O

O

B

–

O

O

OMe

O

NHBn

NHBn

MgBr+

B[(–)-Ipc]2

B[(+)-Ipc]2

OMe,

–78° to rt, 3 h

THF, –78° to rt, 1.5 h MgBr,

OMe B O

Toluene, –78°, 18 h

2.

1.

O

Ether, –78°, 1 h

Ether, –78°, 1 h

Ether, –78°, 1 h

B[(+)-Ipc]2

R = TBDMS

OR

Ether, –78° to 0°, 3 h

Ether, –78°, 1 h

Conditions

B[(–)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

R = Bn

H R = TBDMS

OR

Carbonyl Substrate

Br

OH

OR

OR

I (67)

OR

OR

OH

OH

OH

I

OH

OH

OH (—), 95

(62), 70:30 d.r.

(67)

(67)

(67), 92:8 d.r.

(67)

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

290

299

298

298

298

253

298

Refs.

113

O H

HN

O

N

Me

O

N

Me

BzO

O

O

Cl

R

O

O

O

H

H

O Ph

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B

O

0° to rt

–78° to –25°, 5 h

Ether, THF,

–78° to –25°, 5 h

Ether, THF,

–78° to –25°, 5 h

Ether, THF,

–78° to –25°, 5 h

Ether, THF,

Hexane, –40°

O

N

Me

I

OH

OH

O

HO

HN

O

N

Me

BzO

O

O

N

Me

R

OH

OH

I (79), 85:15 d.r.

O

Cl

9:1 19:1

(94) Cbz

d.r. (96) Boc

R

(55), 97:3 d.r.

(53), 75:25 d.r.

(79), 85:15 d.r.

(83), 70

301

300

300

300

300

122, 244

114

C4

O

TBDMSO

TBDMSO

BnO

TBDMSO

O

O

O

O

O

O

H

H

H

O H

Carbonyl Substrate

B

O

B

O

B

O

B

O

B

O

B

O

O

O

O

O

O

O

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Allylborane Reagent

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Conditions

O

O

TBDMSO

TBDMSO

BnO

BnO

TBDMSO

TBDMSO

O

O

OH

OH

OH

OH

OH

O

O

OH

70:30 d.r.

(82), >97,

(—), 75:25 d.r.

(79), 84:16 d.r.

(83), 96:4 d.r.

74:26 d.r.

(86), >97,

96:4 d.r.

(95), >96,

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

302

302

170

170

302

302

Refs.

115

O

O

O H

B

O

"

B

O

B

O

O

O

O

O

O

OEt

OEt

O

OPr-i

Toluene, –78°, 24-48 h

CH2Cl2, –78°, 24-48 h

4 Å MS, toluene, –78°

CH2Cl2, –78°, 24-48 h

CH2Cl2, –78°, 24-48 h

See table

Toluene, –78°, 24-48 h

OPr-i

O

4 Å MS, toluene, –78°

"

O

O

O

OPr-i

OPr-i

"

B

O

B

O

O

toluene

O

O

I (94), 98:2 d.r. OH

I (—), >300:1 d.r.

I (—), 86:14 d.r.

I (—), 90:10 d.r.

I (85), 90:10 d.r.

(—)

(63), 68:32 d.r.

79:21

87:13

90:10

87:13

90:10

d.r.

(96), >98, 99:1 d.r.

–78° to rt

rt

toluene n-BuLi, THF

rt –78°

CH2Cl2

–78°

I Temp

OH

CH2Cl2

O

OH

Solvent

O

O

TBDMSO

124

124

170

124

124

124

118

302

116

C4

O

O

O

O

O

O

O

O

O H

H

H

O

O

O H

Carbonyl Substrate

O

O

O

O

B(2-d-Icr)2

B[(–)-Ipc]2

B[(–)-Ipc]2

O

OEt

OEt

O

Ether, –75°, 2 h

Ether, –75°, 2 h

–70°

Ether, –78° to rt

–78° to rt, 24 h

4 Å MS, CH2Cl2,

O(Adm-1) Toluene, –78°, 24-48 h

O(Adm-1)

B[(+)-Ipc]2

B

O

B

O

4 Å MS, toluene, –78° O

Toluene, –78°, 24-48 h

O

CH2Cl2, –78°, 24-48 h

"

O

OPr-i

OPr-i

Conditions

"

B

O

Allylborane Reagent

O

O

O

I

OH

OH

OH

OH

I (52), 93:7 d.r.

O

O

O

O

O

(93), >99:1 d.r.

(40), 9:1 d.r.

(60-65), 9:1 d.r.

(72), 6:1 d.r.

309

309

306

305

303, 304

124

170

I (—), 60:40 d.r.

124

124

I (63), 73:27 d.r.

I

(—), 71:29 d.r.

Refs.

I (—), 64:36 d.r.

O

O

OH

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

117

O

O

O

N H

H N

O

TBDMSO

O

Et

MeO

Et

O

O

O

O

O

H

H

H

O

O

O

3

B

B[(–)-Ipc]2

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

O

B[(+)-Ipc]2

THF, reflux, 15 h

Ether, –78°

Ether, –100°, 1 h

4 Å MS, THF

4 Å MS, toluene

2h

Toluene, –78° to rt, O

Et O

OH

O

O

O

TBDMSO

O

Et

MeO

Et

N H

H N

O

OH

OH

OH

I (—), 88:12 d.r.

Et

(90)

(93), >95:5 d.r.

(82), >99

(—), 87:13 d.r.

(75), 95:5 d.r.

293

310

257

170

170

307, 308

118

C5

C4

t-Bu

N H

H N

O H

O

O H

Carbonyl Substrate

I (—), 99 I (—), >99

— THF, –78°, 3 h Ether, –100° a

" B(2-d-Icr)2 "

Ether, –78°, 3 h

I (—), >99

Ether, –100° a

"

TMS

I (88), 83

THF, –78° to rt

I (79), >98

I (60), 99

I (—), 83

THF, –78°, 3 h

"

I

OH

B[(–)-Ipc]2

t-Bu

OH

I

OH (66), 99

(90), 97

(97)

(90)

Product(s) and Yield(s) (%), % ee

I (66), 95

N H

H N

t-Bu

Ether, –100°, 3 h

Pentane, rt, 2 h

Ether, –78°

Ether, –100° a

THF, reflux, 15 h

Conditions

B

BBN

"

B

TMS

B

B[(–)-Ipc]2

3

Allylborane Reagent

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

143

139

240

313

139

136, 136a

240

141

103

312

311

294

Refs.

119 MeO

B

B

B

O

B

O

B O

O

O

N

O

O

O

O

O

O

Ph

O

Ph

N O

N

Bn

O

Bn

OPr-i

OPr-i

O

NHBn

NHBn

Hexane, –40°

Hexane, –40°

67 h

4 Å MS, toluene, –78°,

4 Å MS, toluene, –78°

Toluene, –78°, 18 h

I

I (87), 48

I (85), 45

I (—), 96

t-Bu

OH

I (—), 98

I (—), >99

Ether, –100° a

"

O

I (—), 88

THF, –78°, 3 h O

I (80), 88

THF, –78° to rt

"

I

B(4-d-Icr)2

t-Bu

OH Ether, –100° a

B[(+)-Ipc]2

(56), 86

(—), 99

122

122, 244

131

131, 170

290

139

240

239, 136a

241

120

C5

i-Pr

n-Bu

t-Bu

O

O

O

H

H

H

Carbonyl Substrate

O N

O

SO2Me

B

B

B

O

O N

O

SO2Me

BF3–K+

O

N

O S O

B

B

O

n

n

Allylborane Reagent

Ether, –78° to rt, 2 h

CH2Cl2, H2O, rt, 3 h

15 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

Ether, –78°, 7 h

Ether, –78° to rt, 2 h

CH2Cl2, H2O, rt, 4 h

Conditions

I

OH

i-Pr

n-Bu

t-Bu

OH

OH

OH

I (84), 84

t-Bu

t-Bu

OH

(69), 90

(82)

(95)

(80), 88

(49)

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

133

234

100

245, 246

133

234

Refs.

121

Et

n-Pr

i-Pr

O

O

O

H

O

O

Ph B

Neat, rt, 3 d

O O

THF, –78°, 3 h

B[(+)-Ipc]2

B

THF, –78°, 3 h

Neat, 80-100°

Ether, –78°

Pentane, rt, 2 h

Neat, 0-10°

B[(–)-Ipc]2

B

O

BBN

B

Pentane, rt, 2 h

BBN Pr-n

Neat, 0-10°

BEt2

Et

Et

Et

n-Pr

i-Pr

HO

I (77)

B

O

OH

OH

OH

OH

O

I (100)

I

OH

(—), 62:38 d.r.

(83), 95:5 d.r.

(81), 96:4 d.r.

(87)

(74), 92

(96)

(72)

115

166, 167

166, 167

263

145

103

238

103

238

122

C5

O

O

OR

NH

O

O

OR

Boc

i-Pr

N H

O

H

H

H

R

Carbonyl Substrate

B

B

O

B

O

O

O

B[(+)-Ipc]2

B[(–)-Ipc]2

3

B[(+)-Ipc]2

Allylborane Reagent

Neat, rt, 3 d

Neat, rt, 3 d

Ether, –78°

Ether, –78°

THF, reflux, 2 h

Ether, –78° to rt, 3 h

Conditions

OH

OR

OH

OH

NH

OH

NH

OR

Boc

i-Pr

Boc

i-Pr

N H

HO R

(79)

(53), 81 (44), 79

SiMe2Ph SiMe2Bn

(—)

(—)

MOM

TBDMS

R

MOM

TBDMS

R

(61), 92:8 d.r.

61:39

49:51

d.r.

79:21

79:21

d.r.

(61), 92

TPS

(61), 93:7 d.r.

(32), 59

(72), 89

TES

TMS

R

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

115

115

314

314

293, 294

111

Refs.

123

3

N

O

H

O

O

H

O

O

H

O

H

NH

Cbz

N

Cbz

TBDMSO

Boc

TBDMSO

H

O

O

R = PMB

R = Bn

TBDMSO

RO

H

H

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

—

Ether, –78°

THF, –78° to rt

THF, –100°, 4 h

—

N

3

O

NH

OH

OH

OH

OH

OH

Cbz

N

Cbz TBDMSO

Boc

TBDMSO

OH

TBDMSO

I (93), 95:5 d.r.

Ether, –100° a

"

B[(–)-Ipc]2

I (88), 96

Ether, –100° a

B[(–)-Ipc]2

I

OH

I (75), 96:4 d.r.

RO

THF, –100°

Ether, –100°

"

B[(–)-Ipc]2

(70), 2:1 d.r.

(65), 10:1 d.r.

(60), >95:5 d.r.

(97), >98, 95:5 d.r.

(92), 88

(75), 96:4 d.r

324

274

322, 323

254, 321

319, 320

318

317

316

315

124

C5

TIPSO

BnO

PMBO

OBn

H

O

H

H

H

O

H

H

OMe O

O

OBn O

O

PMBO

O

O

O

O

i-Pr

O

TBDMSO

BnO

TBDMSO

H

Carbonyl Substrate

B

O O

O

O

OPr-i

OPr-i

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

Toluene, –78°

Ether, –78°

Ether, –78°

Ether, –78° to rt

Ether, –78° to rt, 16 h

Ether, –78°, 4 h

2h

Ether, –78° to rt,

Conditions

O

O

TIPSO

BnO

PMBO

OBn

PMBO

i-Pr

O

TBDMSO

BnO

OH

OH

(75), 96:4 d.r

(92), 83

328, 329

327

326

325

264

270

Refs.

(74), 80, 5.5:1 d.r. 330

(74)

(66), 91.5:8.5 d.r.

(94)

(44)

OMe OH

OH

OBn OH

OH

O

OH

TBDMSO

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

125

O

O

S

H

O

H

—

—

Neat, rt, 3 d

O

O N

TBDMSO

O

O

OH

(87), 92

OH

OTES OH

S

H

O

(79), 78

(86), 78

HO

O

O

PMBO

O

O

PMBO B[(–)-Ipc]2

B[(+)-Ipc]2

O

Ether, –93°

–78° to rt

4 Å MS, toluene,

HO

O

PMBO H

O B

O

OPr-i

OPr-i

O

–78° to rt

4 Å MS, toluene,

HO

Boc O

H

H

O

O

O

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B

O

O

Boc

N

TBDMSO

O

OTES O

H

O

O

PMBO

O

O

(82)

(76)

(—), 73:27 d.r.

280, 280a

280, 280a

115

332, 333

331

328, 329

126

C5

O

MeO

O

O

O 3

O

O

PMBO

O

BnO

O

BnO2C

O

O

BnO

O

H

H

O

O

O

OMe O

H

H

H

H

Carbonyl Substrate

B[(–)-Ipc]2

B[(+)-Ipc]2

B(4-d-Icr)2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

Ether, –100°, 1 h

Ether, –78°

Ether, –78°

Ether, –78°

Ether, –78°

Ether, –78°

Conditions

O

MeO

O

O

O 3

OH

OH

OH

OH

OH

PMBO

O

BnO

O

BnO2C

O

O

BnO

O

OMe OH

(88), 96

(80), 94

(95), 78:8 d.r.

(72)

(71), 83:17 d.r.

(75)

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

257

338

337

335

336

335

Refs.

127

C6

n-Bu

O

n-C5H11

O H

O

O

O

N Ts

BBN

"

B

Ts N

0.5 M

B

O

0.5 M

B

O

Ph

Ph

N O

N

CF3

N O

N Cy

CF3

Pentane, rt, 2 h

Toluene, –78°, 2 h

CH2Cl2, –78°, 2 h

5h

4 Å MS, THF, –78°,

t-BuCHO (0.1 equiv),

7h

4 Å MS, toluene, –78°,

t-BuCHO (0.1 equiv),

—

" O

—

B[(+)-Ipc]2

Cy

Pentane, ether, –100°

Pentane, rt, 2 h

B[(–)-Ipc]2

BBN

I

OH

I

n-Bu

OH

I (>90), 95

n-C5H11

I (95), 95

n-C5H11

OH

I

OH

OH

I (91), 88

n-C5H11

n-C5H11

n-C5H11

OH

(100)

(>90), 90

(93), 97

(63), 96

(71), 97

(92)

103

50

50

132

132

339

250

204

103

128

C6

t-Bu

O

O

O

Carbonyl Substrate

CF3

Pr-n

Neat, 0-10°

BEt2

B

Neat, 0-10°

Pentane, rt, 2 h

Pentane, rt, 2 h

BBN

BBN

Neat, 0-10°

BEt2

DMF, –40°, 1 h

(R,R)-i-Pr-DuPHOS, B

CF3

CuF, La(OPr-i)3, O

O

THF, –78° to –40°, 48 h

Ether, –78°

Conditions

O

B

O

B

Ph

Allylborane Reagent HO I

I (88)

I (100)

I

I (94)

t-Bu

HO

I

OH

OH

I (75), 90

t-Bu

(75)

(92)

(99), 91

(70), 99

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

238

103

238

103

238

164

135

145

Refs.

129

t-Bu

O

O

O

SiMe2Ph

SiMe2Ph

Fe(CO)3 H

O

Fe(CO)3 H

Fe(CO)3 H

O

O

O

O

O

B[(+)-Ipc]2

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B

O

O

B[(–)-Ipc]2

B[(–)-Ipc]2

B

Ether, –78° to rt, 3 h

Ether, –78° to rt, 3 h

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Ether, –78° to rt, 18 h

Ether, –78° to rt, 2 h

Neat, 80-100° O

B

t-Bu

OH

OH

OH

OH

(80)

HO SiMe2Ph

HO SiMe2Ph

Fe(CO)3

Fe(CO)3

(4), 41

Fe(CO)3

Fe(CO)3

O

(35), 41

Fe(CO)3

(34), 29

(70), 42

(85-90), 75:25 d.r.

(85-90), 99:1 d.r.

+

(24), 10

OH

111

111

129

129

340

340

263

130

C6

RO

O O

O

O H

H

Fe(CO)3 H

H

OBz O

O

O

O

TBDMSO

N H

H

Carbonyl Substrate

B

O

O

O

B[(–)-Ipc]2

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

O

B[(–)-Ipc]2

3

Allylborane Reagent

—

Ether, –100° to –78°, 3 h

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

—

THF, reflux, 2 h

Conditions

RO

H

O

H

O

O O

(—), 90

(83), 88

65:35

>99:1

d.r.

(—), >98, >50:1 d.r.

PMB HO

(93)

(82), 45:1 d.r.

(79), 89

OH

OH

OH

OBz OH

(50)

TBDMS

R

Fe(CO)3

Fe(CO)3

TBDMSO

N H

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

343

292

342

129

341

293, 294

Refs.

131

EtO

O H

Fe(CO)3 H

MeO

O

O

Pr-i

H

O

HO

O

O

O

TBDMSO

i-Pr

H

O

i-Pr

OH

i-Pr

O

O

O O

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

O

B(OPr-i)2

"

OPr-i

OMe

MgBr+

BF3–K+

– B O O

MeO

–78° to rt, 3 h

MgBr,

i-Pr OMe, THF, –78° to rt, 1.5 h

OMe B O

Ether, –100°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Ether, –10°, 18 h

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

CH2Cl2/H2O, rt, 30 min

n-Bu4NI (10 mol%),

2.

1.

O

I

OH

OH

Fe(CO)3

O

OH

OH

(85-90), 82:18 d.r.

MeO

O

EtO

Fe(CO)3

(81)

(87), 95.5:4.5 d.r.

(97), 65:35 d.r.

(83), 72:28 d.r.

OH

(85-90), 98.5:1.5 d.r.

MeO

O

HO

O HO Pr-i

I (90), 65:35 d.r.

i-Pr

TBDMSO

i-Pr

OH

318

129

129

108

99

276

299

132

C6

i-Pr

O

H

CO2H

4

O

O

MeO

O

O

O H

Fe(CO)3 H

MeO

B(OPr-i)2

B[(–)-Ipc]2

"

B[(–)-Ipc]2

–10° to rt, 13 h

Et3N, CH2Cl2,

Ether, –100°, 1 h

Ether, –78° to rt, 14 h

—

O

O

HO2C i-Pr

MeO

O

I

MeO

I (88)

O

MeO

O Ether, –78° to rt, 2 h

O

O B[(–)-Ipc]2

MeO

O

Fe(CO)3 H

Ether, –78° to rt, 2 h

OH

4

OH

OH

Fe(CO)3

(87)

+

345

344, 340,

253

Refs.

(80), 92

105

257

347

346

345

(82-86), >95:5 d.r. 344, 340,

(28), 52

(33-42), 55

OH

(77)

OH

Fe(CO)3

Fe(CO)3

OH

(91), 92:8 d.r.

Product(s) and Yield(s) (%), % ee OBn OMe OH

MeO

B[(–)-Ipc]2

18 h

Ether, –78° to 0°,

Conditions

O

H

B[(+)-Ipc]2

Allylborane Reagent

O

OBn OMe O

Carbonyl Substrate

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

133

C7

MeO2C O

O

H

4

O H

TMS

O

O

O

O

" 0.03 M

B

O

B

O

N O

N

Bn

O

Bn

OPr-i

47 h

4 Å MS, toluene, –78°,

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

toluene, –78°, 16 h

B

OPr-i

L.A. (10 mol%),

O O

THF, –85°, 18 h

Ether, –100°, 3 h

Ether, –78°

B[(+)-Ipc]2

B

B[(+)-Ipc]2

17 h 2h

47 h –50° rt

(97), 87

97

84

80

(74)

(48)

(—), 87

(—), 94

(40), 97

Sc(OTf)3

AlCl3

L.A.

(66)

(92), 96

(44), 86

Time % Conv.

4

OH

–78°

Temp

I

OH

OH

OH

OH

I (40), 97

I

MeO2C

O

132

131

125

25

348

141

314

134

C7 O H

Carbonyl Substrate

O 0.5 M

B

O

"

B

O

O

O

O

O

" xM

" 0.5 M

B

O

O N

O

OR

OR

O

OPr-i

OPr-i

O

N

Cy

Allylborane Reagent

Cy

4 Å MS, toluene, –78°

Toluene

4 Å MS, –78°

4 Å MS, –78°

t-BuCHO (0.1 equiv),

5h

MeCHO (0.1 equiv), 4 Å MS, toluene, –78°,

4 Å MS, toluene, –78°

Conditions

I

I

I

1h 5h

toluene THF

0.1 0.5

(—), 82 (—), 57 (—), 50

–50° 0° rt

(—), 84 (—), 86 (—), 86

C10H19-c CH(Pr-i)2

(—), 86 Me

(—), 86

(—), 59

Et

(—), 78 CH2Cl2

(—), 82 THF

Pr-i

R

(—), 87

–78°

Temp

I

ether

toluene

(—), 87

(91), 94

(71), 94

(82), 95

(—), 91

(—), 62

Solvent

7h

toluene

0.5

OH

Time

Solvent

3h

5h

Time

x

I (—), 90

I

OH

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

125

131

131, 125

132

132

132

Refs.

135 CF3

O

O

O

O

B

O O

O

OEt

OEt

O

n

NHBn

NHBn

CF3

Ph

O B O

B

O

B

O

B

O

O

O OAc,

O

OEt

OEt

2

CH2Cl2, H2O, rt, 3 h

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

THF, –78°, 1 h

toluene, 40°, 66 h

Pd2(dba)3, DMSO,

O B

O

Toluene, –78°, 18 h

OH

I (53), 92

I (90), 76

I (58), 48

I (—), 99

(92)

234

28

135

349

290

136

C7

xM

0.05 M

xM

0.05 M

O H

Carbonyl Substrate

Bn

O

B

O

B

O

B

O

B

O

O

N

O

N

O

O

Pr-i

O

N

O

N

Pr-i

O

O

O

OPr-i

OPr-i

Allylborane Reagent

Bn

–25°, 40 h

–78°

–78°

–78°

Conditions

I

I

I

29 56

30 CHCl3 0.07

37

% ee 10

18

% Conv.

46

30

27

% ee

THF

toluene

80

14

27

0.07

0.06

Solvent

18 h

CH2Cl2

x

8

16 h THF

40

24

16 h toluene

% Conv.

18 h

CH2Cl2

0.1

Time

20 h

ether

0.08

Solvent

16 h

toluene

Solvent

% Conv.

53

32

21

% ee

59 —

—

Time

78

70

1.5 h

THF

0.08

x

87

95

toluene CH2Cl2

% ee

% Conv.

Time 0.25 h

Solvent

I

OH

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

350

350

350

350

Refs.

137

O

See table

I

B

O O

C6H4NO2-p –78°

I

C6H4NO2-p

CH2Cl2

toluene

15 h

40 h

40 h

40 h

21

94

91

75

80

2

46

46

7

13

4

1

18 h

15 h

85

64

21

95

82

% Conv.

21 h

16 h

5h

6

11

% ee S

R

13

6

11

Time % Conv. % ee

19 h

15 h

20 h

20 h

6

15

S

R

R

S

R

S

S

30

27

23

25

% Conv. % ee

67

CH2Cl2

Time

50

toluene

Solvent % Conv. % ee

Time % Conv. % ee

Time

–58°

–78°

–78°

Temp

Solvent

CHCl3

0.08

0.05 M

CH2Cl2

0.07

Solvent toluene

x

0.08

B

CHCl3

0.15

xM

–78°

CH2Cl2

0.2

–25°

–25°

Temp

–78°

–25°

–25°

–25°

Temp

CH2Cl2

I

OH

CH2Cl2

CH2Cl2

THF

toluene

Solvent

0.1

Ph

See table

I

–25°

O

See table

toluene

Ph

O

O

O

I

OH

Solvent

O

O

O H

H

O

NBn2

–78°, 16 h

x

O

B

O

B

O

B

O

NBn2

0.1

xM

0.08 M

0.06 M

O

350

350

350

350

350

138

C7

0.1 M

0.1 M

O

O

OH

H

Carbonyl Substrate

O

O

N Ts

N

n-Bu3SnH, THF, reflux

n-Bu3P, PhSeCl, AIBN,

15 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

—

B

Ph

Ph

–78°, 2 h

Toluene

Toluene

Conditions

O O

BF3–K+

3,5-(CF3)2C6H3O2S

B

N

Ph

Ph

3,5-(CF3)2C6H3O2S

B

Ts N

B

O

B

O

Allylborane Reagent

I

OH

–25°

–78°

Temp

I (56)

I

OH

I (84), 92

I

I

OH

20 h

15 h

(97)

toluene

CH2Cl2

Solvent

73

15

Time % Conv.

–25°

–78°

Temp 4 46

(>90), 97

(>90), 93

20 h

72 h

Time % Conv.

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

352

100

351

50

350

350

Refs.

139

n-C5H11

n-C6H13

O

i-Pr

O

O

O OH

O

Pr-i

O O

O

B(OPr-i)2

B

O

BBN

BBN

B

O

BBN

B

O

O

OEt

OEt

bmimBr, rt, 3 h

reflux

n-Bu3SnH, THF,

n-Bu3P, PhSeCl, AIBN,

Pentane, rt, 2 h

Pentane, rt, 2 h

Neat, 80-100°

Pentane, rt, 2 h

n-Bu3SnH, THF, –78°

n-Bu3P, PhSeCl, Et3B,

OH

B

+

(94)

(65)

(98)

(30), 8

n-C5H11

OH

OH

(82)

(79)

I + II (100), I:II = 95:5

HO

O

O

OH

n-C6H13

I

i-Pr

i-Pr

OH

II

OH

353

352

103

103

263

103

352

140

C7

BnO

t-Bu

n-Bu

OH

OH

TBDMSO

O

O

H

H

O

TBDMSO

H

O

O

H

H

Carbonyl Substrate

O

B[(–)-Ipc]2

B(OH)2

B(OH)2

B O

OEt

OEt

Ether, –100°

CH2Cl2, rt

CH2Cl2, rt

4 Å MS, toluene, –78°

CH2Cl2, –78°

B[(+)-Ipc]2

O

CH2Cl2, –78°

"

O

4 Å MS, toluene, –78°

Ether, –100°, 2 h

Conditions

B[(–)-Ipc]2

B[(+)-Ipc]2

Allylborane Reagent

BnO

t-Bu

n-Bu OH

OH

TBDMSO

TBDMSO

OH

OH

I

OH

OH

OH

I (73), 2:1 d.r.

TBDMSO

TBDMSO

OH

OH (60), 80

(86), 70:30 d.r.

(84), 68:32 d.r.

(76), 1:1 d.r.

(77), 2:1 d.r.

(98), 9:1 d.r.

(95), 10:1 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

358

110

110

357

357

357

357

356

354, 355,

Refs.

141

PhO2S

Et

O

AcO

TBDPSO

BnO

O

TBDPSO

H

TBDPSO

O

O

H

O

H

H

H

O

O

H

O

H

O

PhO2S

I (75), 88

Ether, –78° a

"

Et

O

AcO

TBDPSO

BnO

OH

TBDPSO

Ether, –100°

Ether, –100°, 0.5 h

Ether, –100°, 2 h a

THF, –78°, 1 h

Ether, –100°

Ether, –78°

4 Å MS, toluene, –78°

TBDPSO

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

O

OH

I

(74), >98

OH

(95), 8:1 d.r.

(62), 86

(80), >90

(80), 96:4

(75), 95:5 d.r.

(91), 97:3 d.r.

OH

OH

OH

OH

H

285

358

188, 671

363

362

361

360

359

142

C7

BnO

TBDMSO 2

O

racemic

OH

O H

H

TBDMS O O

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

Ether, –78° to rt, 2 h

Ether, –78°, 1 h

2. K2CO3, MeOH

1. Allylation

Ether, –78°

Ether, –78°

—

O

I

H

H

TBDMSO

TBDMSO

BnO

O

OH

2

OH

TBDMS OH

Cbz

N

H

OH

OH

TBDMSO

TIPSO

AcO

AcO

H

I (48), 8.6:1 d.r.

O

Cbz

H

O

4 Å MS, toluene, –78°

365

365

364

364

Refs.

(95)

OH 95:5 d.r.

(88),

270

367

(78), >95, 42:36 d.r. 366

(65), 10:1 d.r.

(76), 10:1 d.r.

(85), 4:1 d.r.

Product(s) and Yield(s) (%), % ee

Cbz

O

O

B[(–)-Ipc]2

B

OPr-i

OPr-i

Conditions

N

H

H

O

O

Allylborane Reagent

N

TIPSO

H

O

TBDMSO

O

TBDMSO

TMS

AcO

O

Carbonyl Substrate

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

143

OR

Et

O Fe(OC)3 H

MeO

H

O

O

O

OMe O

O

O

O

R = Me2CHCH2C(O)

MeO2C

Et

O

AcO

RO

OAc O

H

H

H

B[(–)-Ipc]2

B(2-d-Icr)2

B(4-d-Icr)2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

Ether, –78° to rt, 18 h

Ether, –78°

Ether, –78°

Ether, –95°

Ether, –78°, 1 h

Ether, –78°

—

Et

O

O

MeO

MeO

O

MeO2C

MeO2C

Et

O

AcO

AcO

RO

O

O

OH

OH

OH

OH

OH

OH

(17), 54

(35), 62

+

(58), 90

(70), 92

(89), >98:2 d.r.

(48)

(71-79), 5:1-8:1 d.r.

Fe(CO)3

Fe(CO)3

OMe OH

(60), 90:10 d.r.

O

O

OR

OAc OH

340

310

338

193

370

369

368

144

C7

Cl

Ph

O

Bn

O

H

H

H

O

N

H

O

O

H

O H

OTBDMS OTBDMS

O

O

PhMe2Si

PhMe2Si

CO2H

Carbonyl Substrate

TBDMSO

O

O

O

N

O

MeO

n-Pr

O

H

O O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

O

B(2-d-Icr)2

B(4-d-Icr)2

B(2-d-Icr)2

B(OPr-i)2

Allylborane Reagent

Ether, –100°

CH2Cl2, –78°

Ether, –78°, 1 h

Ether, –78°, 1 h

Ether, –78°, 1 h

–10° to rt, 13 h

Et3N, CH2Cl2,

Conditions

Cl

Ph

O

Bn

O

Bn

N

N

O

H

H

H

O

N

OH

OTBDMS

OH

(66), 12:1 d.r.

OH

OTBDMS

O

(62), 80-88

PhMe2Si

(60), 80-88

OH

OH

(80)

PhMe2Si

PhMe2Si

CO2H

TBDMSO

O

O

O

O

O

HO

O

MeO

n-Pr

(91)

(56)

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

374

364

372, 373

372, 373

371

105

Refs.

145

C8

S

N

n-C5H11

n-C7H15

Br

O H

H

H

H

O

O

O

BF3•OEt2 (2 equiv),

BF3–K+

B[(–)-Ipc]2

Ph

O B O

B[(+)-Ipc]2

"

"

bmimBr, rt, 3 h

B(OPr-i)2

Ether, pentane

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

Ether, pentane, –100°

CH2Cl2, H2O, rt, 15 min

n-Bu4NI (10 mol%),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

CH2Cl2, –78°, 15 min

THF, –100°, 1 h

Ether, –100° to –48°

Ether, –78°

"

B[(–)-Ipc]2

B[(+)-Ipc]2 S

N

I (87), 95

n-C5H11

I (94)

I (84)

I (82)

n-C7H15

I (44), 90

n-C7H15

Br

I

OH

I

OH

OH

I

OH

OH

(86)

(85)

(80), 99

(55), 92

(70), 54

380

28

379

99

99

98

353

378

376, 377

375

146

C8

BnO

t-Bu

t-Bu

Ph

O

O

O

H

O

Pr-n

Pr-i

O

O

O

H

H

Carbonyl Substrate

Ether, –80°, 3 h

DMF, –40°, 1 h

B

B[(+)-Ipc]2

La(OPr-i)3, CuF,

(R,R)-i-Pr-DuPHOS,

Pentane, rt, 2 h

O O

BBN

Pentane, rt, 7 d

DMF, –40°, 1 h

BBN

La(OPr-i)3, CuF,

B

(R,R)-i-Pr-DuPHOS,

6h

O, Sc(OTf)3, THF, –78,

CH2Cl2, –78°

Conditions

O O

B[(–)-Ipc]2

B[(+)-Ipc]2

Allylborane Reagent

BnO

t-Bu

n-Pr

t-Bu

OH

OH

OH

OH

HO

i-Pr

Ph

OH (92), 96

OH

(98), 84

(97)

(74)

(65), 93:7 d.r.

(87), 90

(—)

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

382

164

103

103

164

101

381

Refs.

147

Ph

O

OH

OH

H

O

O

O

OTBDMS

n-Bu

i-Pr

PivO

TBDMSO

n-Bu

TBDMSO

H

H

H

H

O

O

i-Pr

O

MeO

O O

– O OMe

MgBr+

"

BF3–K+

B(OH)2

B

O

OPr -i

OPr- i

B[(–)-Ipc]2

B

O

B(2-d-Icr)2

i-Pr

O

OMe B O OMe,

CH2Cl2, rt, 6 h

BF3•OEt2 (5 mol%),

CH2Cl2/H2O, rt, 30 min

n-Bu4NI (10 mol%),

CH2Cl2, rt

–78° to rt, 3 h

THF, –78° to rt, 1.5 h MgBr, 2.

1.

—

–78° to rt

4 Å MS, toluene,

—

OH

OH

OTBDMS

OH

OH

OH

I (91), 65:35 d.r.

Ph

n-Bu

i-Pr

PivO

TBDMSO

n-Bu

HO TBDMSO

I

(94), 65:35 d.r.

(87), 88:12 d.r.

(60)

(70), 80

(77), 70:30 d.r.

OH

OH

(79)

99

276

110

299

385

384

383

148

C8

Ph

O

Ph

O

O

O

Bn

N O

O

H

O

O

OBn O

OMEM

4

H

H

TBDMSO

S

S

TIPSO

O

O

O

H

O

Carbonyl Substrate

H

O

O

O

O

B(4-d-Icr)2

B[(+)-Ipc]2

B[(–)-Ipc]2

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

Allylborane Reagent

Ether, –78°, 1 h a

—

Ether

Toluene, –78°

–78° to rt

4 Å MS, toluene,

–78° to rt

4 Å MS, toluene,

Conditions

Ph

Ph

O

O

O

Bn

4

N O

O

(77), 91

(77), 91

HO

OH

OBn OH

OMEM

TBDMSO

S

S

TIPSO

O

HO

O

HO

331

328, 329

Refs.

OH

(65), 87

(52)

(56), 3:1 d.r.

389, 390

388

386, 387

(64), >90, 14:1 d.r. 330

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

149

O

O

O H

O

OBn

O

OR

R = TBDMS

OR

O

O

H

OTIPS

OTBDMS O

Bu-n OTBDMS

O

MOMO

TBDMSO

OTBDMS

TESO

O

H

H

O H

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

Ether, –78°

Ether, –78°

Ether, pentane, –100°

Ether, –78° to rt, 2 h

Toluene, –78°, 5 h

Ether, –78°

Ether, –78°

O

O

O

OH

O

OBn

O

OTIPS

OR

O

OR

O

OR

OR

OH

OH

(78)

(72), 96:4 d.r.

(84), 96:4 d.r.

(85), 88:12 d.r.

(85), 8:1 d.r.

OH

OH

(79), >19:1 d.r.

OTBDMS OH

(85), 85:15 d.r.

OTBDMS OH

Bu-n OTBDMS

O

MOMO

TBDMSO

OTBDMS

TESO

OTBDMS

TESO

396

396, 397

395

394

393

392, 391

391

150

C8

i-Pr

S

OR

N

O

O

MOMO

O H

O H

O

OMOM

OTBDMS

R = TBDMS

OR

O

TBDPSO

O

O

H

O H

Carbonyl Substrate

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

Allylborane Reagent

Ether, –100°, 0.5 h

CH2Cl2, –78° to rt

Ether, –78°, 3 h

Ether, –78°

Ether, –78°

Conditions

OR

O

OR

O

S

i-Pr

OR

OR

N

O

OH

OH

I

OH

O

OH

(83)

(88), >19:1 d.r.

(80), 96:4 d.r.

(89-96), >97

OH

(74), 88:12 d.r.

OMOM

OTBDMS

O

MOMO

TBDPSO

O

O

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

188, 400

399

398

396

396

Refs.

151

C9

PMBO

I

O

O

H

O H

B

B

O O

TMS

Ph

Ether, –100° to –78°,

B[(–)-Ipc]2

Hexane, –40°

Ether, –78°, 3 h

3h

Pentane, ether, –100°

2h

Ether, –95° to –100°,

B[(+)-Ipc]2

"

2ha

Ether, –95° to –100°,

Ether, –100°

B[(–)-Ipc]2

B[(–)-Ipc]2

—

"

I

I (81), 24

I (92), 97

OH

I

OH

OH

O

I (72), 93:7 d.r.

I

PMBO

I (83), >95

I (96), >91

(73), 94

(72), 92

(89), 97:3 d.r.

122

143

292

204

192

403, 192

402

401

152

C9 O H

Carbonyl Substrate

CF3

O

– +

N Ts

"

Ph

Ph

CF3

BF3 K

B

Ts N

B

CH2Cl2, H2O, rt, 15 min

n-Bu4NI (10 mol%),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

–78°, 2 h

THF, –78°, 1 h

toluene, –78°, 24 h

B

O

L.A. (10 mol%),

O O

bmimBr, rt, 3 h

Conditions

B(OPr-i)2

Allylborane Reagent

CH2Cl2

toluene

Solvent

Sc(OTf)3

AlCl3

L.A.

I (95)

I

I (74)

(69)

I

OH

(>90), 98

(>90), 97

I

OH

I

OH

(91)

(98), 76

(84)

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

100

99

50

135

25

353

Refs.

153

BnO

n-C5H11

C 6F 5

MeO

O

O

H

O

H

H

O

O

H

O

H

H

B(OPr-i)2

Ph

O B O

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

O,

bmimBr, rt, 3 h

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

1h

Pentane, ether, –100°,

—

–78°, 6 h

Sc(OTf)3, THF,

n-C5H11

3h

Ether, –100° to –78°,

Ether, –78°, 2 h

BnO

n-C5H11

C6F5

MeO

OH

OH

OH

OH

OH

OH

(77), 93

(85), 82:18 d.r

(64), 97

(76), 96

(75), 94

(80), 97

(74), 93

OH

353

27, 28

251

405

101

292

404

154

C9

Cy

OH

O

OH

N

Bu-t

TBDMSO

Ph

O

O

t-Bu

O

H

O

O

O

Ph

H

H

H

Carbonyl Substrate

O

B(OH)2

"

BF3–K+

B(OH)2

B

O

BBN

BBN

Allylborane Reagent

CH2Cl2, rt

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

30 min

CH2Cl2, H2O, rt,

n-Bu4NI (1 mol%),

CH2Cl2, rt

CH2Cl2, rt, 16 h

Pentane, rt, 2 h

Octane, 125°, 5 d

Conditions t-Bu

OH

N

OH

Cy

OH

I

OH

OH

OH

OH

(94), 65:35 d.r.

(85), 72:28 d.r.

(70)

(85), 67:33 d.r.

(25)

(85)

Ph

I (86), 70:30 d.r.

TBDMSO

Ph

O

HO

t-Bu

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

110

347

276

110

235

103

103

Refs.

155

O

O

O

O

PMPO

TBDMSO

i-Pr

PMBO

i-Pr

TBDMSO

HO

HO

HO

O

O

Cy

H

O

Ph

H

Ether, pentane, –100°

O

PMPO

TBDMSO

i-Pr

PMBO

i-Pr

O

OH

OMEM

Ph

OH

OH

OH

OH B[(+)-Ipc]2

Ether, pentane, –100°

Ether, pentane, –100°

Ether, –90° to rt

O HO Cy

O HO C6H13-n

TBDMSO

HO

HO

HO

O HO Ph

O

B[(+)-Icr]2

B[(+)-Icr]2

B[(+)-Ipc]2

Ether, –78° to rt, 14 h

Ether, –10°, 18 h

Ether, –10°, 18 h

Ether, –10°, 18 h

OPMP

H

H

B[(–)-Ipc]2

B(OPr-i)2

B(OPr-i)2

B(OPr-i)2

OPMP

O

H

O

C6H13-n

Ph

OMEM

O

O

O

(71), 10:1 d.r.

(84)

(75), 97.5:2.5 d.r.

(—), 96:4 d.r.

(—)

(70)

(80)

(89)

407

407

407

406

347

108

108

108

156

C9

O

Bn

N O

O

TBDMSO

O

O

O

O

Ph

O

Ph

O

H

H

H

O H

O

Carbonyl Substrate

H

O H

O

B(2-d-Icr)2

B(4-d-Icr)2

B[(–)-Ipc]2

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

O

B[(–)-Ipc]2

Allylborane Reagent

Ether, –78°, 1 h

Ether, –78°, 1 h

Ether, –78°

a

a

Ether, pentane, –100°

Ether, –78°

Ether, 18°

Conditions

O

Bn

O

Bn

N

N

O

O

O

O

TBDMSO

O

O

O

O

O

O

Ph

OH

Ph

OH

Ph

OH

OH

OH

OH

O H H (71), >95:5 d.r.

(—)

(89), 11:1 d.r.

(50), 1:1 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

(52)

(56)

389

389, 373, 390

310

407

408

408

Refs.

157

Ph

O

PMBO

O

TBDPSO

O

O

TBDPSO

MeO

O

O

OMe O

OR

O

H

OAc

H

racemic

H

O

H

O O

H H

H

H

H

TBDMS O

H

O

H

OTBDMS

OBn OBn O

H

O

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

Ether, –78°

THF, –78°

3.5 h

THF, –78° to rt,

Ether, –78°

Toluene, –78° a

Ether, –78°

Ph O

PMBO

O

TBDPSO

O

O

H

O

OH

H

(65-70), 95:5 d.r.

O OH

H

OTBDMS

(73), >15:1 d.r.

OBn OBn OH

H

(95)

(92)

414, 415

413

412

(72) 411

(42)

409, 410

TES

OH

(41) +

310

TBDMS

R

OH

TBDMS OH

OH

O

H OAc

OMe O

OR

H

OAc

O H H (71), >95:5 d.r.

TBDPSO

TBDPSO

MeO

O

158

C10

C9

n-C9H19

Me

N

O

Boc

O

H

H

CO2Et O

OMOM

Bn

H

O

MeO2C

O

O

TBDMSO

O

H

O O

OMe

OTBDMS

Carbonyl Substrate

TMS

B(2-d-Icr)2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B

B[(+)-Ipc]2

Allylborane Reagent

Ether, –50°, 17 h

Pentane, ether, –100°

THF, –78° to rt, 3.5 h

Ether, –78°

Ether, –100°, 3 h

Ether, –100°, 2 h

Conditions

O

I

O

OMe

OTBDMS

(70), 95

O

(74), 92

(64), 95:5 d.r.

(80), 89

OH (95), 9.5:1 d.r.

OH

Boc

I (22), 76

n-C9H19

Me

N

OH

OMOM

O

TBDMSO

Bn

O

MeO2C

HO

O

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

423

204

420, 421, 422

419

418

416, 417

Refs.

159

Ph

n-C7H15

n-C6H13

O H

O H

H O

O

O

O

O

O

O

O

B[(–)-Ipc]2

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B

O

B

O

"

B

O

CONMe2

–78°, 6 h; work-up

O, BF3•OEt2, THF,

Ph

–78°, 6 h

O, Sc(OTf)3, THF,

Ph

toluene, –78°

Cr(CO)3, 4 Å MS,

toluene, –78°

Cr(CO)3, 4 Å MS,

4 Å MS, toluene, –78°

Toluene, –78°, 24 h

CH2Cl2, –78°, 24 h

Ph

Ph

I

OH

OH

(85-95), 92

(55-70), 31

(55-70), 70

(48), 93 (80), 96

NH4Cl NaOH, H2O2

(96), 96

(36), 47

OH

OH

OH

Work-up

n-C7H15

n-C6H13

n-C6H13

I (29), 28

n-C9H19

OH

101

101

128

130

130

424

424

160

C10

Ph

O H

Carbonyl Substrate

O

O

B N Ts

Ts N

B

O

"

"

Ph

Ph

O

OPr-i

OPr-i

B[(–)-Ipc]2

Allylborane Reagent

O,

–78°, 6 h

O, BF3•OEt2, THF,

Ph

O, L.A., THF, –78°, 6 h

Ph

O, L.A., THF, –78°, 6 h

Ph

–78°, 6 h

Sc(OTf)3, THF,

Ph

O, Sc(OTf)3, THF, 6 h

Ph

Conditions

(18), 83 (33), 94 (65), 94 (92), 96 (59),96

Ag(OTf) Y(OTf)3 Sc(OTf)3 BF3•OEt2

(40), 27 (70), 47

none BF3•OEt2

L.A.

(28), 96

SnCl4

I

Sm(OTf)3

L.A.

I (33), 37

I

I

I (88), 96

Ph

OH (96), 97 (100), 95 (100), 89 (100), 86

–78° –78° –78°

(94), >98

–78°

–96°

Temp

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

101

101

101

101

101

Refs.

161

MeO

Ph

R

O

NO2

H

O

O

H

H

O OH

"

B

O O

O

O

OEt

reflux

n-Bu3SnH, THF,

n-Bu3P, PhSeCl, AIBN,

n-Bu3SnH, THF, –78°

n-Bu3P, PhSeCl, Et3B,

reflux

B

n-Bu3P, PhSeCl, AIBN,

3h

n-Bu3SnH, THF,

OEt

O,

Ether, –100° to –78°,

–78°, 6 h

Sc(OTf)3, THF,

R

–78°, 4 h; –70°, 36 h

O, Sc(OTf)3, THF,

O O

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

Ph

I (85), 46

MeO

MeO

Ph

R

OH

NO2

OH

OH

I

OH

OH

(73), 91

(61), 73

(80)

(35), 96

352

352

352

292

(68), 96 101

NO2

101

OMe

R

(88), 96

162

C10

Ph

Ph

Ph

Ph

O

O

O

O

H

O

H

H

H

H

Carbonyl Substrate

B

O O

O

O

OPr-i

OPr-i

B[(–)-Ipc]2

B(2-d-Icr)2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

Toluene, –78°

—

Ether, –78°, 4 h

Ether, –78°

Ether, –78°

Ether, –78°

Ether, –78°

Conditions

Ph

Ph

Ph

Ph

Ph

Ph

OH

OH

OH

OH

OH

OH

OH

(94), 81:19 d.r.

(—)

(63), 98.5:1.5 d.r.

(74), 74:26 d.r.

(74), 97:3 d.r.

(72), 98:2 d.r.

(72), 67:33 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

427

426

425

166, 167

166, 167

166, 167

166, 167

Refs.

163

Ph

Ph

O

O

O

O

H

H

O H

CF3

CF3

DMF, –40°, 1 h

O

(R,R)-i-Pr-DuPHOS,

48 h

THF, –78° to –40°,

B

CF3

CF3

La(OPr-i)3, CuF,

O

O

48 h

THF, –78° to –40°,

Neat, 0-10°

Neat, 0-10°

Neat, 0-10°

Neat, 0-10°

O

B

O

B

O

BEt2

BEt2

BEt2

BEt2

HO

Ph

HO

I (98), 50

Ph

Ph

I

OH

OH

OH

OH

(96), 67

(91), 76

(97)

(84)

(80)

(73)

164

135

135

238

238

238

238

164

C10

Ph

MeO

t-Bu

O

OEt

(85) (90) (90)

p-Tol 4-(t-Bu)Bn DMPM

(80)

(80)

R

Bn

R

I

(80)

HN

OH

OH

(94)

Ph

I (61), 73

I

Ac

CH2Cl2, rt

n-Bu3SnH, THF, –78°

n-Bu3P, PhSeCl, Et3B,

n-Bu3SnH, THF, reflux MeO

n-Bu3P, PhSeCl, AIBN,

OH

Ts

O

OEt

I

+ t-Bu I + II (100), I:II = 55:45

OH II

88:12

99:1

85:15

85:15

80:20

79:21

80:20

d.r.

(85), 46

(80)

OH

Product(s) and Yield(s) (%), % ee

4-(t-Bu)Bn, DMPM

BBN

"

B

O

n-Bu3SnH, THF, reflux MeO

O

n-Bu3P, PhSeCl, AIBN, O

O

t-Bu

B

Pentane, rt, 2 h

Conditions

Boc

R

O

OH

BBN

Allylborane Reagent

R = Boc, Ts, Ac, Bn, p-Tol,

HN

O

O

Carbonyl Substrate

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

107

352

352

352

103

Refs.

165

HO

Ph

BnO

O

OH

9

O

R = Bz

O

O

H

Ph

H

B(OPr-i)2

B(OH)2

B[(–)-Ipc]2

Ether, –10°, 18 h

CH2Cl2, rt

Ether, –78°, 1.5 h

Base, CH2Cl2, rt

HO

Ph

BnO

I

–78°

toluene toluene

45 h

Et3N

OH

9

Ph

OH

45 h

DBU

OH

15 h

d.r.

93:7

91:9

94:6

92:8

83:17

84:16

53:47

88:12

85:15

74:26

(83), 73:27 d.r.

(65)

(29)

(26)

d.r. 52:48

(66), 92

0°

CH2Cl2

(85)

–78°

CH2Cl2

Time

0°

ether

—

Base

0° –78°

ether

–78°

Temp

Solvent THF

91:9

0°

85:15

CH2Cl2 toluene

THF

73:27

ether

d.r. 52:48

THF

Solvent

O HO

I (—)

—

"

B(OPr-i)2

I (—)

rt

BBN

108

110

316

107

107

107

166

C10

MeO

O

O O

O

Bn

N

H

BnO

TBDMSO

BnO

n-C5H11

HO

O

O

O

H H

O

O

Tol

O

H

O

H

O

H

H

O

H

O

O

H

Carbonyl Substrate

O O

B(4-d-Icr)2

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B[(–)-Ipc]2

B[(–)-Ipc]2

B(OPr-i)2

Allylborane Reagent

Ether, –78°, 1 h a

THF, –78°

Toluene, –78°

Ether, –78°

Ether, –78° to rt

Ether, –10°, 18 h

Conditions

MeO

O

O

Bn

BnO

N O

O

H

TBDMSO

BnO

n-C5H11

HO

O

O

(79)

H

OH

OH

(56)

(82), >10:1 d.r.

(78), 8:1 d.r.

OH

OH

OH

(83)

(73), 85:15 d.r.

H H

O

O

O HO Tol

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

390

431, 432

430

429

428

108

Refs.

167

C11

O

O

O

O

n-C10H21

Ph

N

TBDMSO

O

H

TBDMSO

TBDMSO

O

H

Ether, –100° to rt,

O

O

OH

O

O

Br

O

B

O O

B[(+)-Ipc]2

B[(–)-Ipc]2

B(2-d-Icr)2

toluene, –78°, 16 h

L.A. (10 mol%),

2h

Ether, –78° to rt,

2h

Ether, –78° to rt,

Ether, –78°, 3 h

1.5 h

N O

HO

O

n-C10H21

Ph

Ph

N

HO

TBDMSO

TBDMSO

TBDMSO

O

O

Br

OH

(52), 4:1 d.r.

(71), 98

(71), >20:1 d.r.

Sc(OTf)3

AlCl3

L.A. (73)

(54)

(89-91), 96:4-92:8 d.r.

(89-91), 96:4-92:8 d.r.

TBDMS OH

OH

O

O B[(+)-Ipc]2

Ether, –78° 2

H

B[(+)-Ipc]2

2

H

TBDMS O

O

H

O

25

435

435

434

261

433

168

C11

O 2N

1-Adm

Ph

Ph

OH

O

O

H

OMe

H

H

OMe

OMOM

O

n-C10H21

O

O H

Carbonyl Substrate

O

O

B[(–)-Ipc]2

B

O

B[(–)-Ipc]2

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

O

Allylborane Reagent

O, Ph

Ph

— O2N

OH

OMe

(54)

OMe

OMOM

OH

OH

OH

(82), 9:1 d.r.

(92), >95, 1:1 d.r.

(83), 96

(86), 86

Product(s) and Yield(s) (%), % ee

OH

n-C10H21

n-Bu3SnH, THF, reflux 1-Adm

n-Bu3P, PhSeCl, AIBN,

6h

Sc(OTf)3, THF, –78°,

Ph

6h

O, Sc(OTf)3, THF, –78°,

Ph

4 Å MS, toluene, –78°

Conditions

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

436

352

101

101

125

Refs.

169

TBDPSO

Et

O H

TBDMSO

O

OH

OH

BnO

i-Pr

Ph

Ph

OTBDPS

OTBDMS

O

H

H

OH

O

O

H

O H

B[(+)-Ipc]2

B[(–)-Ipc]2

B(OH)2

B(OH)2

B[(–)-Ipc]2

"

B[(–)-Ipc]2

Ether, –78°

—

CH2Cl2, rt

CH2Cl2, rt

Ether, –78°, 4 h

Ether, –78°, 4 h

Ether, –100°, 1 h a

TBDPSO

OH

OH

(92), 3:1 d.r.

OH

OH

OH

(—)

(90), 60:40 d.r.

(63), 93

(84), 90:10 d.r.

OH

I (70), >20:1 d.r.

TBDMSO

OH

OH Et

BnO i-Pr

Ph

Ph

OTBDPS

I (79), >96

OTBDMS

OH

364, 441

440

110

110

439

438

437

170

C11

O

O

O

O

MeO2C

BnO2C

O

PMP

TBDMSO

O

O H

OTES O

O

O

PMBO

H

O

O

H

H

Carbonyl Substrate O H

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

Allylborane Reagent

Ether, –100°, 2 h

THF, –78° to rt, 2 h

Ether, –78°

Ether, –100°

Ether, –78°, 1 h

Ether, –78°

Conditions

O

O O

O

MeO2C

BnO2C

BnO2C

O

PMP

TBDMSO

O

OH

OH

OH

OTES OH

(87), 17.6:1 d.r.

O

OH

(—), 2:1 d.r.

O

OH

(62)

(74), 81:19 d.r.

(85), 95:5 d.r.

(80), >10:1 d.r.

O

PMBO

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

416, 417

445

444

444

443

442

Refs.

171

C12

i-Pr

9

HO

N H

Ph

Ph

H

H

O

O

O

O

H OMOM

O

OBn OBn OBn O

O

Pr-n

n-C11H23

PMBO

TBDMSO

Ph

O

H

B

B(OH)2

3

B[(–)-Ipc]2

"

"

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

CH2Cl2, rt

THF, reflux, 2 h

3h

Ether, –100° to –78°,

Ether, –78°

6h

Ether, –78° to 0°,

Ether, –100°

THF, –78°

Ether, –90°

Ether, –90°

i-Pr

N H

Ph

(83)

OH

OH

I

OH

HO Ph

9

OMOM

OH

OMOM

OH

(94)

(69)

(89), 92:8 d.r.

(71), 91

(84), 91

(67), 15:1 d.r.

OBn OBn OBn OH

O

O

Pr-n

I (60), 90

I (75), 99

n-C11H23

PMBO

TBDMSO

Ph

O

TBDMSO

Ph

O

110

293, 294

292

449

448

447

413

446

446

172

C13

C12

O

OTBDPS

BnO

i-Pr

O

O

O

O

O

O

Br

H

O

O

Bu-t

H

H

Carbonyl Substrate

B[(–)-Ipc]2

BEt2

BEt2

B(2-d-Icr)2

"

B[(–)-Ipc]2

Allylborane Reagent

Ether, –78°, 4 h

Neat, 0-10°

Neat, 0-10°

Ether, –78°

Ether, –78°

CH2Cl2, –78° to rt

Conditions

O

OTBDPS

BnO

I (67)

i-Pr

O

O

OH

OH

I

O

Br

OH

(84)

OH

(86)

(90)

(48)

(92), >98:2 d.r.

OH

Bu-t

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

451

238

238

450

326

399

Refs.

173 2

OR

MeO2C

O

OR

OMOM

OMe

R = TBDMS

O

OMe O

R = TBDMS

MeO

H

OMe

OMe

H

OMe OR

O

H

O MeO

OMe

H

OTES O

2

O

OAc O

TIPS OR

O

O

H

H O

BEt2

B[(+)-Ipc]2

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

O

B[(+)-Ipc]2

B[(+)-Ipc]2

Ether, –10°

Ether, –100°

Ether, –100°

5h

4 Å MS, toluene, –78°,

Ether, –90°, 1 h

6h

Ether, THF, –78° to rt,

MeO2C

MeO

O

TIPS OR

O

TIPS OR

OMOM

O MeO

OMe

OH 2

OTES OH

(80), >98, >15:1 d.r.

2

OR

2

OH

OAc OH

(80), >98, >15:1 d.r.

2

OR

OMe

OH

OH

O

(>70), 91:1 d.r.

OMe O

OH

(77), >19:1 d.r.

(55), >99:1 d.r.

OR

OMe OMe OMe OR

HO

(94)

458

457

457

456, 297

455

454

452, 453,

174

C14

C13

OPr-i

OPr-i

n-C5H11

n-C5H11

O OMe

O

4

O

OMe O

O

O

2

O

OH

O

O

O

O

H

H

OH

O

O

n-C11H23

BnO

H

O

O

Carbonyl Substrate

H

O

O

OBn

H

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B(OH)2

B(4-d-Icr)2

Allylborane Reagent

Ether, –78°, 1.5 h

Ether, –78° to rt

Toluene, –78°

Ether, –78°

CH2Cl2, rt

Ether, –78°, 2 h

Conditions

O

OPr-i

OPr-i

n-C5H11

n-C5H11

O

n-C11H23

BnO

OMe

O

4

O

2

OH

(60), 71

O

OMe OH

O

O

OH

OH

(71), 20:1 d.r.

O

OH

O

O

OH

(90)

(99), 5:1 d.r.

HO

O

(88), 65:35 d.r.

OBn

(93), 94:6 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

460

428

459

433

110

434

Refs.

175

C15

NC

Ph

O

4

Ph

O

O

O

O

2

H

O

OTIPS

O

n-C14H29

BnO

O

O

O

H

H

H

O H

O H

O O O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B(2-d-Icr)2

Ether, –78° to rt

1h

4 Å MS, toluene, –78°,

Ether, –78°

Ether, –78°

Ether, THF, –100°, 4 h

Ether, –100°, 1 h

Ether, –78°

NC

Ph

Ph

O

4

Ph

Ph

OH

O

O

OH

OH

(—), 3.5:1 d.r.

(—), 2.5:1 d.r.

(87), >19:1 d.r.

OH

OH

OH (78)

(92), >97:3 d.r.

(75), 92

OH

(75), >10:1 d.r.

O

O

O

2

OTIPS

O

4

O

n-C14H29

BnO

464

463

444

444

462

461

450

176

C16

C15

O

O

O

MeO

O

O

O

O

O

CO2Me

O

O

OTBDMS

O

H O

3

B

B[(–)-Ipc]2

B[(–)-Ipc]2

Toluene, 20°, 0.5 h

Ether, –78°

Ether, –100°, 2 h

HO

O

O

MeO

O

O

O

HO

O

OH

O

(98)

(65), 77:23 d.r.

O

OTBDMS

(74), 90:5 d.r.

O

OAc

Ether, –78°, 3 h

CO2Me

OH

OH

(77), 9:1 d.r.

Product(s) and Yield(s) (%), % ee

OAc

B[(–)-Ipc]2

Conditions

OTBDMS

H

H

Allylborane Reagent

OTBDMS

O

O

Carbonyl Substrate

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

467

466

416, 417

465

Refs.

177

C17

Ph

O

O

MOMO

OBn OBn

6

H

O O

AcHN OTBDMS OBn

O

H

OPMP

H

OMOM

O

H

H

O

O

OBn

OMe

TBDMSO

OPr-i

OPr-i

Ph

O

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

THF, –78° to rt, 18 h

23 h

Ether, THF, –78° to –20°,

23 h

Ether, THF, –78° to –20°,

Ether, –78°, 1.5 h

6h

O, Ph Sc(OTf)3, THF, –78°,

Ph

OPr-i

OPr-i

Ph

O

HO

MOMO

OBn OBn

6

OH

OMOM

O

O

(70)

(52), >97.5:2.5 d.r.

(65), 58

(94), 95

468

468

460

101

O (48), 6:1 d.r. 469, 470 AcHN OTBDMS OBn

OH

OPMP

OH

OH

OBn

OMe

TBDMSO

Ph

178

C18

C17

MOMO

Ph

i-Pr

O

Ph

O

O

H

O H

O

O

H

Carbonyl Substrate C6H4Br-p

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

Ph

–78° to –20°, 23 h

Ether, THF,

4 h; –70°, 36 h

O, Sc(OTf)3, THF, –78°,

Ph

6h

O, Sc(OTf)3, THF, –78°,

Ph

Ph

Ether, –78°

Conditions

MOMO

Ph

Ph

i-Pr

O

Ph

Ph

OH

OH

OH

O

O

(48), 3:1 d.r.

(76), 93

(23), 93

OH

(78)

C6H4Br-p

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

468

101

101

326

Refs.

179

C20

H

n-C14H29

AcO

H

O

H

O

OTBDMS

TBDMSO

O

OTBDMS

OTBDPS

n-C14H29

H

O

H

H

OH

O

SO2Ph

O

H

Ether, –100°, 1 h

n-Bu3SnH, THF, reflux

B[(+)-Ipc]2

n-Bu3P, PhSeCl, AIBN,

O

0.5 h

Ether, pentane, –100°,

Ether, –100°

–78° to –20°, 23 h

Ether, THF,

B O

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

H

O O

OTBDMS

OH

OH

n-C14H29

AcO

OTBDMS

TBDMSO

H

H H

HO

OH (64)

(88), 72:28 d.r.

OH

SO2Ph

(55), 96:4 d.r.

(54), 6:1 d.r.

OTBDPS (70), >20:1 d.r.

n-C14H29

MOMO

461

352

471

461

468

180

C23

C22

C20

MOMO

n-C14H29

n-Pr

H

O

TBDMSO

O

H

2

O

2

H

H

O

H

OMOM

6

H

H

H

O

OMe O

OTBDMS

OMe

n-C14H29

TBDMSO

n-C10H21

MOMO

Carbonyl Substrate

H

O

H H

O

O

B[(–)-Ipc]2

B[(–)-Ipc]2

O

OPr-i

OPr-i

B[(+)-Ipc]2

BBN

B

O

O

Allylborane Reagent

Ether, –100°

Toluene, –78°

Ether, –100°, 1 h

—

3h

4 Å MS, toluene, –78°,

Conditions

2

H

6

O

(83), 88:12 d.r.

2

OMe OH

OH

(88), 88:12 d.r.

H

OH

OH

OH

H

H H MOMO OMOM (78), >95:5 d.r.

n-C14H29

TBDMSO

H

O

OTBDMS (65), 95:5 d.r. OMe

n-C14H29

TBDMSO

n-Pr

O

(78), 3.8:1 d.r.

n-C10H21

MOMO

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

475

474

461

473

472

Refs.

181

C24

AcO

n-Pr

OMe

n-C14H29

MOMO

MOMO

n-C14H29

H

HO

2

O

H

O H O

H

O

H

7

OMe O

OMOM

MOMO

H

H

H

O

O

O

H

H

n-Bu3P, PhSeCl, AIBN, n-Bu3SnH, THF, reflux

O

Toluene, –78°

Ether

Ether

Ether, –100°

B O

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

AcO

H

O

O

O

OMe

7

H

H

H H

OH

(95), 86:14 d.r.

2

OMe OH

OMOM (95), 96:4 d.r.

n-C14H29

MOMO

n-Pr

O

MOMO

H

OMOM (91), 96.5:3.5 d.r.

n-C14H29

MOMO

MOMO

n-C14H29

H

(79), 52:48 d.r.

OH

OH

O

(50), >95:5 d.r.

OH

352

474

476

476

475

182

C32

C24

a

CO2Me

H

O

H

CO2Me

H

O

The reaction mixture was free of Mg2+ ions.

N

HN

N

NH

N

H

NH

HN

H

H

O

N

CO2Me

MeO2C

AcO

H

HO

Carbonyl Substrate

O

B(OH)2

B(OH)2

B

O

O

O

OEt

OEt

Allylborane Reagent

0.33 h

CH2Cl2, ether, 0°,

0.33 h

CH2Cl2, ether, 0°,

n-Bu3SnH, THF, –78°

n-Bu3P, PhSeCl, Et3B,

Conditions

H

NH

N

CO2Me

CO2Me

MeO2C

AcO

N

HN

N

NH

H

H

HN

N

H

OH

OH

H

(95)

(95)

CO2Me

OH

(60), 85:15 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) A. NON-AROMATIC CARBONYL SUBSTRATES (Continued)

477

477

352

Refs.

183

C5

O

Cl

O

Me

N

N

PMBO

N

O

O

O

O

H

H

O

N

H

O

H

O

H

Carbonyl Substrate

N Ts

Ph

Ph

BEt2

B[(–)-Ipc]2

B[(+)-Ipc]2

B

Ts N

B[(–)-Ipc]2

Allylborane Reagent

Neat, 0-10°

Ether, –100°, 1 h

Ether, –100°

CH2Cl2, –78°

Ether, –100° to rt, 18 h

Conditions

O

Cl

N

O

Me

N

PMBO

N

OH

OH

O

HO

O

N

OH

(92)

(78), >99

(84), >95

OH

(44), 92

(—), >95

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES

238

478

374

280

378

Refs.

184

C5

S

O

O

O

O

H

H

O

H

Carbonyl Substrate

O

B[(–)-Ipc]2

B(2-d-Icr)2

B[(–)-Ipc]2

BF3–K+

B

O

B[(–)-Ipc]2

B

n

Pr-n

Allylborane Reagent

Ether, –100°, 1 h

Ether, –100°, 1 h

Ether, –100°, 1 h

15 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

CH2Cl2, H2O, rt, 6 h

Ether, –100°, 1 h

Neat, 0-10°

Conditions

I

S

O

HO

O

HO

I (95)

I

O

O

O

OH

OH

OH

OH

(80), 90

(88), >99

(80), >91

(88)

(91), >99

(71)

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

478

478

478

100

234

478

238

Refs.

185

C6

N

S

S

O

O

O

H

H

SiMe2Ph

O

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

Ether, –100°, 1 h

THF, –100°, 1 h

Ether, –78° to rt, 3 h

Ether, –100°, 1 h

B(2-d-Icr)2

Ether, –100°, 1 h

Ether, –100°, 1 h

n

CH2Cl2, H2O, rt, 14 h

Ether, –78°, 3 h

B[(+)-Ipc]2

B[(–)-Ipc]2

B

O

TMS B

I

N

N OH

OH

S PhMe2Si

OH

OH

I (83), >99

S

HO

S

HO

S

I (86), 97

(84), >99

(94), 94

(81), 17

(90), 79

(75), 82

(95)

478

480, 481

111

478

479

478

234

143

186

C6

N

R1

R2

N

N

O

O

H

H

O H

Carbonyl Substrate

O

O O

n

NHBn

NHBn

B(4-d-Icr)2

B

O

B

O

O

B[(–)-Ipc]2

B[(+)-Ipc]2

Allylborane Reagent

Ether, –100°, 1 h

CH2Cl2, H2O, rt, 3 h

Toluene, –78°, 18 h

Ether, –100°, 1 h

Ether, –100°, 1 h

Conditions

N

N

OH

N

N

OH

OH

I (92), 94

R1

R2

OH

(73), 90 (75), 91.5 (78), 88

Cl MeO H

H MeO

(78), >99

(79)

(85), >99

(74), 85.5

H

Cl

(75), 66

Cl

(94), 94

Br

H

R2 H

H

R1

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

478

234

290

478

479

Refs.

187

C7

O

H

S

O

O

S

H

O

H

3,

Ph Bn

Et Et

I (83), 95

COPh

Bu

I (76), 98

COPh

Ether, –100°, 1 h

R2

R1

S

6h

16 h; 4 h

4h

Time

(59)

(74)

(68)

(93), >98, 98:2 d.r.

rt; 50° 45 h; 17 h (47)

rt

rt; 40°

rt

Temp

(89)

OH

(84), 85

Et

I

OH

—

Pd(PPh3)4,

OR2,

I (96)

I (95)

I

OH

HO

"

THF

BR1

Pentane, rt, 2 h

Neat, 0-10°

–70° to 130°

THF, –100°, 4 h

S

HO

B[(+)-Ipc]2

B(R )2

1

BBN

B(Bu-n)2

3

B

B[(–)-Ipc]2

CuF, La(OPr-i)3, DMF, –40°, 1 h

O

O B

(R,R)-i-Pr-DuPHOS,

479, 484

250

483

103

238

262, 1

482

164

188

C7 O H

Carbonyl Substrate

B

TMS

93 94

0° –25°

I (—), 94 I (—), 96

I (—), 87 I (—), 98

Ether, –78°, 3 h Ether, –100° a

THF, –78°, 3 h Ether, –100° a

" "

B(4-d-Icr)2 "

I

(81), 96

90

rt

% ee

(—), 95

Product(s) and Yield(s) (%), % ee

Temp

OH

I (82), 90

I (—)

Ether, –78° to rt

Ether, –78°

Ether, 3 h

I (80), >98

I (—), >99

I

OH

B[(–)-Ipc]2

B

Ph

"

Ether, –100° a

"

Ether, –78°, 3 h

THF, –78°, 3 h

Conditions

B(2-d-Icr)2

Allylborane Reagent

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

139

240

139, 289

240

136, 136a

145

143

143

139, 241

240

Refs.

189 O

O

B

O

B

O

O

O

O

MeO

B

O

"

B

O

NHBn

NHBn

MeO

CONMe2

See table

12 h

4 Å MS, CH2Cl2, –78°,

12 h

4 Å MS, CH2Cl2, –78°,

Toluene, –78°, 24 h

CH2Cl2, –78°, 24 h

toluene, –78°, 16 h

B

O

L.A. (10 mol%),

O O

Ionic liquid, rt, 3 h

B(OPr-i)2

I

OH

Sc(OTf)3

AlCl3

L.A.

I

(85)

TEAN

18 h 14 h

–78° –78° toluene

14 h ether

14 h –20° toluene

Time

(87.8), 90

(87), 83

(80.5), 46

(77.7), 34

(88)

emimBr

(76), 59

(89)

bmimBF4

0°

Temp

(80)

(88)

(87)

bmimBr

Ionic liquid

toluene

Solvent

I (72), 23

I (62), 19

I (82), 37

I

I

OH

290

485

485

424

424

25

353

190

C7 O H

Carbonyl Substrate

O

O

O B O

B Ph

Ph

L.A. (10 mol%)

Hexane, –40°

CH2Cl2, –78°, 2 h

Sc(OTf)3 (10 mol%),

toluene, –78°

Cr(CO)3, 4 Å MS, 4 Å MS, toluene, –78°

O

4 Å MS, THF, –78°

"

O

O

OPr-i

OPr-i

Conditions

"

"

B

O

Allylborane Reagent

I

CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 toluene hexane

TfOH Cu(OTf)2 Yb(OTf)3 Sc(OTf)3 Sc(OTf)3 Sc(OTf)3

–78°

–78°

–78°

–40°

–40°

–78°

–78°

–78°

CH2Cl2 AlCl3 TiCl4

rt

Temp CH2Cl2

Solvent

(78), 72

none

L.A.

I (90), 36

I (100), 7

I (—), 60

I (90), 83

I

OH

2h

2h

2h

2h

2h

2h

2h

2h

72 h

20

30

90

4

4

72

22

14

50

8

46

92

38

52

84

78

63

11

Time % Conv. % ee

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

27, 28

122

27, 28

131

128

125

Refs.

191

O

O

O

Ph

O B O

Ph

O B O

B

O

N

O

O

O

MeO

B

B

O

B

O

Ph

O

O

N

Bn N Bn

CH2Cl2, –78°, 2 h

Sc(OTf)3 (10 mol%),

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

Ether, –78° to rt

Hexane, –40°

CH2Cl2, –78°, 2 h

Sc(OTf)3 (10 mol%),

47 h

4 Å MS, toluene, –78°,

I (100), 84

I

OH

I (92), 88

I (76), 46

I (100), 9

I (—), 85

(85), 92

27, 28

27, 28

486

122

27, 28

131

192

C7

O H

Carbonyl Substrate

O

B

O

B

O

"

B

O

O

O

O

O

O

O

NHR

NHR

O

OEt

OEt

O

OPr-i

OPr-i

Allylborane Reagent

O OAc,

O

OPr-i

OPr-i

2

O OAc,

O

OEt

OEt

2

See table

toluene, 20°, 63 h

Pd2(dba)3, DMSO,

O B

O

4 Å MS, –78°

toluene, 20°, 44 h

Pd2(dba)3, DMSO,

O B

O

Conditions

I

72

THF

–60° –78° –78°

toluene THF toluene Ph

THF Bn Ph

–40°

ether Bn

rt

Solvent Ph

Temp

59

59

CH2Cl2

60

ether

% ee

toluene

Solvent

(63), 42

R

I (83), 45

I (—)

I

OH

18 h

14 h

16 h

16 h

18 h

Time

(82.3), 80

(76.2), 72

(83.5), 85

(79.6), 61

(62.5), 6.4

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

290

349

125

349

Refs.

193

O

"

B N Ts

Ts N

B

O

N

SO2Me

B

N

Ts N

O

O

B

3,5-(CF3)2C6H3O2S

B

N

Ph

Ph

R

3,5-(CF3)2C6H3O2S

R

Ph

Ph

–78°

Ether, –78° to rt, 2 h

Toluene, –78°, 2 h

Toluene, –78°, 2 h

CH2Cl2, –78°, 2 h

THF, –78°, 1 h (91), 74 (91), 86 (90), 46 (89), 62 (94), 60 (92), 66 (92), 80 (90), 50 (90), 96

Me Ph 4-MeOC6H4 3,5-Me2C6H3 3,5-(t-Bu)2C6H3 3,5-(CF3)2C6H3 2-naphthyl CF3

(88), 74 (90), 81

THF ether

Solvent

I (91), 88

I (92), 96

I (>90), 95

I

(50), 42

I

H

R

I (>90), 94

I

245, 246

133

351

50

50

135

194

C7 O H

Carbonyl Substrate

O

O

O

O

N

N

N B

S

B

S

B

MeO2S

B

O

O

O

O

Ts N

Ts N B O

Ph

Ph

Ph

Ph

Allylborane Reagent

Ether, –78°, 7 h

Ether, –78°, 7 h

Ether, –78°

Ether, –78°, 7 h

Ether, –78°, 7 h

Conditions

I

OH

I (93), 75

I (90), 66

I (93), 75

I

OH

(93), 75

(89), 71

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

245, 246

245, 246

246

245, 246

245, 246

Refs.

195

B

THF, –70°, 17 h

CH2Cl2, –40° to rt

2

BX2•OEt2

B

CH2Cl2, –40° to rt

O

Neat, 80-100°

Ether, –78°, 7 h

See table

BX2

B

O

S O N B O

O

O

O S N

O

I

I

I

(93), 85

–78°

ether

(53)

(67) (38)

Cl Br

X

(57) Br

I

OH

O

Cl

X

(91), 72

–78°

toluene

B

(96), 88

–100°

THF

(—), 18

(81)

(92), 74

(94), 78

–78°

OH

(91), 65

–40°

THF

Temp

THF

O

Solvent

97

97

487

263

245, 246

245, 246

196

C7

O 2N

O

O

O

OH

R

H

Carbonyl Substrate

O

B

O

B

O

O

O

OEt

O

OEt

OAc,

O

O

O

OAc,

O

OEt

OEt

2

toluene, 20°, 22 h

Pd2(dba)3, DMSO,

O B

O

toluene, 20°, 21 h

Pd2(dba)3, DMSO,

O

B B

reflux

B

O

n-Bu3SnH, THF,

n-Bu3P, PhSeCl, AIBN,

See table

Conditions

O O

BBN

Allylborane Reagent

O2N

O2N

pentane

NMe2

OH

rt

68°

rt

rt

Temp

(92), 49

(73)

hexane

OEt

OH

pentane

OC(O)Ph

(79)

pentane

OH

Solvent

Cl

2

R

OH

(89) (82) (59) (91)

2h 2h 50 h 3h

Time

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

349

349

352

103

Refs.

197 B

O

B

O

B

O

B

O

O

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OEt

OEt

O

NMe2

NMe2

O OAc,

O 2

NMe2

NMe2

O OAc,

O

OEt

OEt

2

O OAc,

O

OPr-i

OPr-i

2

O OAc,

2

toluene, 20°, 21 h

Pd2(dba)3, DMSO,

O B

toluene, 20°, 20 h

Pd2(dba)3, DMSO,

O B

O

toluene, 20°, 19 h

Pd2(dba)3, DMSO,

O B

O

toluene, 20°, 21 h

Pd2(dba)3, DMSO,

O B

O

I (62), 1

I (76), 45

O2N

I (73), 3

I

OH (83), 53

349

349

349

349

198

C7

MeO

O 2N

H NO2

O

O

O

H

H

Carbonyl Substrate

CH2Cl2/H2O, rt, 15 min

n-Bu4NI (10 mol%),

toluene, –78°, 36 h

B

BF3–K+

L.A. (10 mol %),

THF, –78° to rt, 2 h

15 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

15 min

L.A., CH2Cl2, –78°,

Conditions

O O

B[(–)-Ipc]2

BF3 K

– +

BF3–K+

Allylborane Reagent

MeO

MeO

MeO

O2N

NO2

OH

OH

OH

OH

OH

(99)

(0)

(41) (93)

BF3•OEt2

(98)

Sc(OTf)3

AlCl3

L.A. (84)

(82)

(28)

SnCl4

(72), 89

(20)

TMSCl

(16)

Ti(OPr-i)4

AlCl3

B(OMe)3

L.A.

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

100

25

488

100

99

Refs.

199

Br

HO

Br

Cl

O

O

H

H

O

O

H

H

BF3–K+

B[(–)-Ipc]2

B(OPr-i)2

B[(–)-Ipc]2

BF3–K+

B[(–)-Ipc]2

CH2Cl2/H2O, rt, 15 min

n-Bu4NI (10 mol%),

THF, –78° to rt, 2 h

bmimBr, rt, 3 h

Ether, –78° to rt, 3 h Br

OH

(58-73)

HO

Br

Cl

OH

OH

(97) (97)

Ph3PMeCl

(99)

(77), 94

(86)

(98)

Et3NBnCl

(99)

n-Bu4NBr

(15)

n-Bu4NI

PTC none

OH

OH

CH2Cl2/H2O, rt, 15 min Br

Br

(58-73)

PTC (10 mol%),

Ether, –78° to rt, 3 h

OH

100

488

353

489

100

489

200

C7 H

R = H, MeO, MeS, O2N

R = H, MeO, Cl, O2N

R R = MeO, O2N

O

Carbonyl Substrate

CF3

O

O CF3

"

BF3–K+

B

O

B

O

B

TMS

n

Allylborane Reagent

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

CH2Cl2, –78°, 15 min

BF3•OEt2 (2 equiv),

CH2Cl2, H2O, rt

THF, –78°, 1 h

Ether, –78°, 3 h

Conditions

I

I

R

I

R

(95) (90) (96)

MeO MeS O2N

(91) (89) (93) (95)

H MeO MeS O2N

R

(93)

H

R

I

OH

(96), 92

(93), 94

Cl O2N

(93), 94

(90), 96

MeO

H

R

I

OH

4h 3h

Cl O2N

7h

6h MeO

Time H

(87), 97

O2N

R

(90), 96

MeO

R

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

(90)

(85)

(93)

(87)

99

98, 99

234

135

143

Refs.

201

O

F

F

R1

H

AcO

F

F

R2

N

O

F

O

OAc

H

H

H

O

O

H

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

"

BF3–K+

B[(–)-Ipc]2

THF, –100°, 4 h

–100°, 2 h

Ether/pentane,

—

CH2Cl2, –78°, 15 min

BF3•OEt2 (2 equiv),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

–78°

F

F

F

F

I

R1

AcO

F

F

F

F

HO

Cl

R1

I

OH

F

N

OH

F

OH

MeO

Cl

R2

OH

R2

OAc

OH

OH

(84)

(85)

(89), 99

(86), 97

HO

Cl

R1 (85)

(86)

(95), >98, 96:4 d.r.

MeO

Cl

R2

(76), 90

254, 482

491

250

98

99

490

202

C8

C7

O

EtO2P

R3

R2

R4

R1

R5

O H

O H

Carbonyl Substrate

B[(–)-Ipc]2

B(2-d-Icr)2

B[(+)-Ipc]2

Allylborane Reagent

–78°

Pentane, ether, –100°

Pentane, ether, –100°

Conditions

EtO2P

O

I (—)

R3

R2

H H F H H F

H F H H F H

F H F F H H

OH

F

F

R3

R2 R1 F

H

H

H

F

H

H

F

H

H

F

H

F

F

H

H

F

H

H

F

H

H

H

F

F

F

F

F

R4

H

R3

I

R2

R5

OH

R1

R4

R1

H

H

H

H

F

H

F

H

H

H

H

H

F

F

R5

98

97

96

96

98

97

96

% ee

(90), 98.0

(85), 95.0

(80), 98.1

(86), 95.3

(90), 95.2

(88), 99.6

(86), 99.8

(98)

R4

H

H

H

H

H

F

F

R5

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

492

248, 249

248

Refs.

203

CF3

n-Bu

N

MeO2C

NC

O

O

O

H

O

H

O

H

H

CF3

B

O

B

O

B

O

O

O

O

CF3

B[(–)-Ipc]2

"

BF3–K+

n

THF, –78°, 1 h

CH2Cl2, rt, 16 h

CH2Cl2, H2O, rt, 4 h

Ether, –78° to rt, 3 h

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

CH2Cl2, –78°, 15 min

BF3•OEt2 (2 equiv),

CF3

n-Bu N

MeO2C

MeO2C

I (95)

NC

O

OH

OH

OH

I

OH

OH

(100)

(95)

(58-73)

(94), 94

(95)

135

235

234

489

99

98, 99

204

C8

R

R

H

CF3

O

O H

O SiMe2Ph

R = MeO2C, NC

R = CF3, Me

O

Carbonyl Substrate

BBN

B(2-d-Icr)2

B[(+)-Ipc]2

B[(+)-Ipc]2

Pentane, rt, 2 h

Pentane, ether, –100°

Pentane, ether, –100°

Ether, –78° to rt, 3 h

CH2Cl2/H2O, rt, 15 min

n-Bu4NI (10 mol%),

toluene, –78°

B

BF3–K+

L.A. (10 mol%),

Conditions

O O

Allylborane Reagent

I CF3

HO

(98)

(97)

97 97

meta para

(100)

96

ortho

Isomer

para

meta

ortho

(81), 95.2

(80), 99.9

24 h

24 h

16 h

16 h

Time

(96), 96.8

(65), 26 Me

Isomer

(81), 36 CF3

R

Sc(OTf)3

AlCl3

Me Me

Sc(OTf)3

AlCl3

L.A.

CF3

CF3

R

% ee

HO SiMe2Ph

OH

NC

MeO2C

R

I (—)

R

I

R

I

OH

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

(62)

(47)

(69)

(80)

103

248

248

111

100

25

Refs.

205

O

CF3

B

O

B

O O CF3

B(OPr-i)2

Neat, 80-100°

–78° to –40°, 48 h

bmimBr, rt, 3 h

DMF, –40°

B x equiv

La-additive, CuF,

(R,R)-i-Pr-DuPHOS,

THF, –78° to rt

O

B[(–)-Ipc]2

I

I

3

O

15

3

B O

HO

HO

3 15

1.2

15

15

3

3

x % Cat.

HO

1h

3.5 h

20 h

Time

(60), 96

(90)

(88), 92 toluene

20 h

THF

Solvent

(83)

(S)-BINOL-La(OPr-i)3

(R)-BINOL-La(OPr-i)3 20 h

La(OPr-i)3

La(OPr-i)3

none

La-additive

(63), 5

(48), 79

(52), 80

(94), 82

(95), 77

(42), 79

263

135

353

164

166

206

C8

O

O

Ph

Br

R = MeO, Cl

R = MeO, Br

R = H, O2N

HO2C

R

O

Carbonyl Substrate

B

CF3

CF3

Ph

CF3

B(OPr-i)2

–10° to rt, 13 h

Et3N, CH2Cl2,

48 h

B CF3

THF, –78° to –40°,

O O

48 h

B O

THF, –78° to –40°,

Ether, –78°

Ether, –78°

Conditions

O

B

Ph

Allylborane Reagent

O

HO

HO

HO Ph HO2C

R

R

R

HO

O2N

(96), 98

Br

Cl

(94)

(87), 92

(95), 98 (94), >98

MeO

R

(89), 94

MeO

R

(92), 96 (90), >98

H

R

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

105

135

135

145

145

Refs.

207

C9

R1

R2

H

H

O

O

O

O

O

O

H

H

O

O

H

H

Ph B

DMF, –40°, 1 h

B

Ether, –78°

La(OPr-i)3, CuF,

(R,R)-i-Pr-DuPHOS,

THF, –100°, 4 h

THF, –100°, 4 h

THF, –100°, 4 h

THF, –100°, 4 h

O O

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

R1

R2

HO

HO

OH

OH

OH

OH

OH

OH (94), >98, 99:1 d.r.

H

Me

R1

(70), 94

OH

Me

H

R2 (83), 83

(89), 84

(89), >98, 94:6 d.r.

(91), >98, 99:1 d.r.

(94), >98, 99:1 d.r.

OH

145

164

254

254

254

254

208

C11

C10

O Ph

H

O

OMe OMe

OMe OMe O

t-Bu

Fe

O

N

O

H

H

Carbonyl Substrate

B[(+)-Ipc]2

BBN

B(OPr-i)2

Ether, –78°, 30 min

Pentane, rt, 4 h

bmimBr, rt, 3 h

Ether, –100°, 1 h

DMF, –40°, 1 h

B

B[(+)-Ipc]2

La(OPr-i)3, CuF,

(R,R)-i-Pr-DuPHOS,

Conditions

O O

Allylborane Reagent

OH

(82)

N

(82)

OH

(88), 85

OMe OMe

OMe OMe OH

t-Bu

Ph

Fe

HO

(78), 82

(75), 92

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

493

103

353

479

164

Refs.

209

C15

C14

C13

Ph

Cy

Ph

Ph

OH

HO

Ph

O

OH

O

O

O

O

Ph

H

Ph

Ph

H

TBDMS O

OMe OTBDMS

OMe O

B(OH)2

B(OH)2

B(OPr-i)2

BBN

BEt2

B(OPr-i)2

B[(–)-Ipc]2

CH2Cl2, rt

CH2Cl2, rt

–10° to 40°, 15 h

Et3N, CH2Cl2,

Pentane, rt, 2 h

Neat, 0-10°

bmimBr, rt, 3 h

Ether, –78° to rt, 2-3 h

Ph

I

OH

HO

Ph

HO HO Ph

OH

HO Ph

HO HO Ph

Cy

Ph

I (100)

Ph

TBDMS OH +

OTBDMS

(93), 86:14 d.r.

(90), 91:9 d.r.

(84), 72

OMe OTBDMS

OMe OH

(94), >99:1 d.r.

(79)

(86)

OMe OTBDMS (—)

OMe O

110

110

109

103

238

353

494

210

C17

C16

H

H

HO

TBDMSO

H

HO

Ph Ph

H O OTBDMS

OTBDMS

O

O

O

Carbonyl Substrate

B

B[(+)-Ipc]2

3

3

B

B(OH)2

Allylborane Reagent

THF

0.5 h

CH2Cl2, –78° to rt,

0.5 h

CH2Cl2, –78° to rt,

CH2Cl2, rt

Conditions HO Ph

TBDMSO

H

HO

Ph

0.01 M

1:3

d.r.

(60)

(85)

(93)

(98)

>99:1

>99:1

(95), 86

0.08 M

1:3

OH OTBDMS

0.08 M

0.08 M

Conc.

(87)

1:2

1:1

All3B/Ald

2:1

1:1 (85)

(93), 92:8 d.r.

All3B/Ald

OTBDMS

OH

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 1. ADDITION OF UNSUBSTITUTED ALLYL REAGENTS (Continued) B. AROMATIC AND HETEROAROMATIC CARBONYL SUBSTRATES (Continued)

7:1

1.8:1

1.5:1

1:1

d.r.

495

487, 464

487, 464

110

Refs.

211

C19

C18

a

OR

N H

N H

N H

The reaction mixture was free of Mg2+ ions.

O

O

TBDMS O

R = TBDMS

OR

OMe

OMe

OMe O

O

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

3

B

THF

THF

THF

CH2Cl2, 40°, 5 h

OR

OMe

OMe

OR HO

O HO

TBDMS

OMe HO

OH

0.04 M

2:1

N H

N H

N H

0.04 M

1:1 (95)

(90)

(93)

(75)

(95), 90

(95), 90-95, 1:1 d.r.

(95), 69

0.08 M

1:1

Conc. 0.08 M

1:2

All3B/Ket

d.r.

>99:1

>99:1

>99:1

>99:1

495, 496

495, 496

496

487, 464

212

C2

C1

H

O

O

H

H

Carbonyl Substrate

B(4-d-Icr)2

"

B[(–)-Ipc]2

B

TMS

B(2-d-Icr)2

"

B[(+)-Ipc]2

B(Bu-n)2

BBN

Ether, –78°, 3 h

THF, –78°, 3 h

Ether, –78°, 3 h

Ether, –78°, 3 h

Ether, –78°, 3 h

Ether, –78°, 3 h

THF, –78°, 3 h

Neat, 0-5°

Pentane, rt, 2 h

Conditions

(72), 96, >99:1 d.r.

(92)

(88)

Product(s) and Yield(s) (%), % ee

(75), 90, >99:1

I (—), 94, >99:1 d.r.

I (75), 95, >99:1 d.r.

I

OH

I (68), 95, >98:2 d.r.

I (75), 94, >99:1 d.r.

I (72), 92, >99:1 d.r.

I

OH

OH

HO

TABLE 2. ADDITION OF Z-CROTYL REAGENTS Allylborane Reagent

497

137

497

143

497

497

137

238

103

Refs.

213

RO

O

O

R = TBDMS

R = Bn

H R= Bn

R

B

TMS

O

O O

O

Ph

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

BBN

"

B

"

B

THF, –78°, 12 h

THF, –78°

THF, –78°, 3 h

Pentane, rt, 2 h

Hexanes, –55° to –20°

—

Ether, –78° to rt

—

Ether, –78°, 3 h

I

OH

I

OH

I (86), 94

RO

RO

OH

2

I (93), 95:5 d.r.

(97)

(93)

(80)

(70), >90, >20:1 d.r.

OAc

Cl

R

I (93), 60-70, 98:2 d.r.

I (20), 97:3 d.r.

I (92), 97:3 d.r.

I (68), 95, >98:2 d.r.

505

503, 504,

502

295

273, 500,

103

499

498

22

3

143

214

C3

C2

RO

O

O

H

H

H R= TBDMS

O

Carbonyl Substrate

B(2-d-Icr)2

"

B[(+)-Ipc]2

B(4-d-Icr)2

"

B[(–)-Ipc]2

B

B[(–)-Ipc]2

Ph

O B O

Ether, –78°, 3 h

THF, –78°, 3 h

THF, ether, –78°, 3 h

THF, –78°, 3 h

THF, ether, –78°, 3 h

THF, –78°, 3 h

THF, –78°, 4 h

THF, –78°, 3 h

CH2Cl2, –78°, 24 h

Sc(OTf)3 (10 mol%),

Conditions

I

OH

OH

OH

(73), 86, 93:7 d.r.

(63), 90, >99:1 d.r.

(57), 96, >49:1 d.r.

(70), 95-96, 98.5:1.5 d.r.

I (78), 96, >99:1 d.r.

I (78), 92, 99:1 d.r.

I

OH

I (75), 94, >99:1 d.r.

I (70), 95-96, 98.5:1.5 d.r.

I (70), 90, 99:1 d.r.

RO

Product(s) and Yield(s) (%), % ee

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

497

137, 497

506

137, 497

506

137, 497

142

137

27, 28

Refs.

215

TES

CF3

O

O

O

O

B

O

CF3

H

O H

O

O O O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B(Bu-n)2

BBN

B(Bu-n)2

B

O

B(OMe)2

THF, –78°, 4 h

4h

4 Å MS, toluene, –78°,

Neat, 0-5°

Pentane, rt, 2 h

Neat, 0-5°

Ether, –78° to rt

Ether, –78° to rt

TES

CF3

O

O

B

CF3 OH

I (100)

I

OH

OH

(88)

(82)

(62), 96:4 d.r.

(85)

OH

I (20), 97:3 d.r.

I

OH

(43), 80

356

354, 355,

507

238

103

238

22

43

216

C3

R = Bn

R = PMB

R = TBDMS

R= TBDMS

R = TBDMS

O

R = 3,4-DMB

H R = TBDPS

TBDPSO

RO

O

H

Carbonyl Substrate

B

O O

O

O

OPr-i

OPr-i

B(2-d-Icr)2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

4h

4 Å MS, toluene, –78°,

THF, –78°

THF, –78°, 3 h

—

3h

BF3•Et2O, THF, –78°,

THF, –78°

THF, –78°

THF, –78°, 5 h

THF, ether, –78°

THF, –78°

Conditions

I

OH

RO

I (62)

OH

I (82), >98, >99:1 d.r.

I (—)

TBDPSO

I (78), 90

I (72), 97, >95:5 d.r.

I (82)

I (72), >97.5:2.5 d.r.

RO

OH

(68), 72, >98:2 d.r.

(81)

(82), 90

Product(s) and Yield(s) (%), % ee

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

519, 37

518

501

517

533

515

514

512, 513, 501

511

510

508, 509,

Refs.

217

H

H

H

H

R = Bn

OR R = TES

O

OBn

O

NBn2

O

NHBoc

O

R = TBDPS

O

BIpc2(+)

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B

O

B[(–)-Ipc]2

B[(+)-Ipc]2

Ph

O B O

–78°

THF, ether, –78°, 1.5 h

THF, –78°, 3 h

THF, –78°, 3 h

Neat, rt, 4 d

—

—

CH2Cl2, –78°, 24 h

Sc(OTf)3 (10 mol%),

OH

I

OR

OR OH

OH

OBn

OH

OBn

OH

NBn2

OH

I (—), 1:1 d.r.

BocNH

RO

OH

(83), 98.5:1.5 d.r.

(75), >99:1 d.r.

(74), 90, 73:27 d.r.

(78), 92, 99:1 d.r.

(50), 51:49 d.r.

(—), >97:3 d.r.

(57), 96, >49:1 d.r.

523

522

167

167

521

520

520

27, 28

218

C3

OR

H

O

O

O

N

O

THF, –78°, 4 h

THF, rt, 72 h

O

O N

OH

I (95), 95:5 d.r.

TBDMSO

OH

I (98), >99:1 d.r.

I

B

B

THF, –78°, 4 h

O O

O

I

OH

OH

B

30 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

CH2Cl2, rt, 6 h

BF3•OEt2 (5 mol%),

1.5 h

4 Å MS, toluene, –78°,

OR

OH

Boc

H

H

O

"

O

OPr-i

OPr-i

Neat, rt, 4 d

I

(66), 57:1 d.r., 93:7 syn:anti

(65), 5.3:1 d.r., 97:3 syn:anti

(46), 75:25 d.r.

(73), 95:5 d.r.

(98), 88:12 d.r.

Product(s) and Yield(s) (%), % ee

O

O

H

O

O

O

BF3–K+

B

O

B

O

Conditions

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

Boc

TBDMSO

O

R =TBDPS

R= Bn

O

Carbonyl Substrate

142

142

525

276

99

524

521

Refs.

219

HO

O

O

O

O

O

O

O

O

O

O

Ph

CF3

N O

N

CF3

N O

N

Ph

B(OPr-i)2

racemic

B

B

B

O

B

O

B

O

B

CF3

CF3

–10° to rt, 36 h

Et3N, CH2Cl2,

–78° to rt, 18 h

Petroleum ether,

–78° to rt, 18 h

Petroleum ether,

12 h

4 Å MS, toluene, –78°,

–78° to rt, 10 h

4 Å MS, toluene,

24-48 h

CH2Cl2, –78° to rt,

THF, –78°, 4 h

HO

HO

I (—), 97:3 d.r.

I (86), >99:1 d.r.

I (58), 61:39 d.r.

I (95), >99:1 d.r.

(65), 94:6 d.r.

I (75-85), 96:4 d.r., 94:6 syn:anti

I (57), 4.2:1 d.r., 96:4 syn:anti

106

288

288

132

132

118

142

220

C4

C3

i-Pr

n-Pr

O

O

EtO2C

HO2C

H

H

O

O

Carbonyl Substrate

O O

OPr-i

OPr-i

B

O

B

B

O

TMS

B(OC6H13-n)2

BF3–K+

B

O

O

B(OPr-i)2

Ether, –78°

THF, –78°, 4 h

Ether, –78°, 3 h

Ether, rt

–78°, 2 h

BF3•OEt2, CH2Cl2,

–78° to rt, 6 h

4 Å MS, toluene,

–10° to rt

Et3N, CH2Cl2,

Conditions

I

OH

OH

(70), 93, 96:4 d.r.

(91), 94, >98:2 d.r.

(79)

(90), >98:2 d.r.

(87), 9, 5.4:1 d.r.

(96), 99:1 d.r.

Product(s) and Yield(s) (%), % ee

I (51), 94:6 d.r.

i-Pr

n-Pr

n-Pr

OH

EtO2C

HO

EtO2C

HO

HO2C

HO

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

22

142

143

31

98

134

106

Refs.

221

RO

O

H

H

R = PMB

R = TBDPS, TBDMS

R = TBDMS

R = TBDMS, TBDPS, Bn

R = Bn

Cl

O O

O

B

O

B

O

O

O

O

O

CF3

N

O

OPr-i

OPr-i

O

N

B[(+)-Ipc]2

B

O

B[(–)-Ipc]2

CF3

18 h

4 Å MS, toluene, –78°,

–78° to rt, 10 h

4 Å MS, toluene,

THF, –78°, 3 h

Toluene, rt

THF, –78°, 3 h

I (—)

RO

RO

I (—)

RO

I (70)

THF, –90°, 16 h

"

I

OH

86:14

81:19

84:16

Syn:Anti

— 96:4

TBDMS (83) 95:5

d.r. Syn:Anti TBDPS (74) >99:1

R

(75), >95:5 d.r.

61:39

Bn OH

53:47

TBDPS

d.r. 62:38

TBDMS

(83), 92:8 d.r.

(78), 95:5 d.r.

(71), 90:10 d.r.

R

I

OH

I (70), 87.5:12.5 d.r.

–78°, 4 h

"

I

OH

I (73)

RO

Cl

OH

Ether, THF, –100°

THF, –78°, 3 h

Neat, rt, 4 d

"

B[(+)-Ipc]2

B

O

531

132

250

169, 297

167

530

529

527, 528

167, 295

521

222

C4

H

H R = TES

O

R = Bn

O H

R = TBDPS, TBDMS

R = TBDMS, TBDPS, Bn

OR

RO

RO

O

Carbonyl Substrate

O

O

O

O

O

B[(+)-Ipc]2

"

B[(–)-Ipc]2

CF3

N O

N

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B

O

B

O

O

CF3

THF, ether, –78°, 3 h

THF, –90°, 16 h

THF, –78°, 3 h

THF, –78°, 3 h

–78° to rt

4 Å MS, toluene,

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Conditions

10 h

TBDMS

I

OH

OH

12 h

OR

I

OH

Bn

95:5 99:1 63:37

(—), 94:6 d.r.

(—), 99:1 d.r.

(82)

90:10

88:12

86:14

Syn:Anti

53:47

73:27

88:12

d.r.

TBDPS

97:3

89:11

d.r. Syn:Anti

(—) 91:9

TBDMS 53:47

R

(90)

Bn

TBDPS (—) 97:3

96:4

d.r. Syn:Anti

TBDMS (71) 99:1

R

(41), 3:1 d.r.

Time

TBDPS

R

I (—)

OH

I (72), 9:1 d.r.

RO

RO

I

RO

RO

OH

Product(s) and Yield(s) (%), % ee

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

522

269

167

167

132

169

169, 297

Refs.

223

O

PMBO

O

O

TBDPSO

MeO

O

O

H

H

H

O

OMe O

O

R = MOM

H

B

O O

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

24-48 h

CH2Cl2, –78° to rt,

THF, –78°, 4 h

THF, –78°, 4 h

THF, –78°, 6 h

THF, –78°, 2 h

Ether, THF, –78°, 3 h

O

TBDPSO

TBDPSO

O

O

PMBO MeO

O

OH

OMe OH

OMe OH

OH

OH

I (—), 3:1 d.r.

97:3 syn:anti

(75-85), 98:2 d.r.,

(72), >97.5:2.5 d.r.

(70), >97.5:2.5 d.r.

(98)

(76)

537, 118

536

536

354, 355

534, 535

532

224

C5

C4

Et

t-Bu

HO2C

O

O

Et

H

H

O

O

Carbonyl Substrate

B

TMS

O

O

O

OPr-i

OPr-i

B[(–)-Ipc]2

BF3–K+

B

O

B

B(OPr-i)2

B(OPr-i)2

Ether, –78°, 3 h

CH2Cl2, H2O, rt, 15 min

n-Bu4NI (10 mol%),

7d

4 Å MS, toluene, –78°,

Ether, –78°, 3 h

THF, –78°, 4 h

Neat, 0-5°

–10° to rt

Et3N, CH2Cl2,

Conditions

I

OH

OH

Et

OH

I (96), >98:2 d.r.

I (66), 70, 99:1 d.r.

I (92), 94, >98:2 d.r.

t-Bu

HO2C

HO Et

(73), 82:18 d.r.

(75), 97, 95:5 d.r.

(81)

(92), 99:1 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

538, 167

100

519, 37

143

142

238

106

Refs.

225

Et

racemic

O H

racemic

B

B

racemic

B

B

"

"

B

O

O

O

O

O

O

O

O

O

O

Ph

Ph

Ph

Ph

B[(+)-Ipc]2

–78° to rt

Petroleum ether,

–78° to rt

Petroleum ether,

–78° to rt

Petroleum ether,

–78° to rt

Petroleum ether,

Neat

–78° to rt

Petroleum ether,

Neat, rt, 3 d

Ether, –78°, 3 h I

OH

Et

Et

Et

Et

I (—)

OH

OH

OH

OH

70:30 69:31 68:32

42° 61° 81°

(94), 66:34 d.r.

(95), 70:30 d.r., >99:1 syn:anti

(90), 70:30 d.r., >99:1 syn:anti

(74), 55:45 d.r., >99:1 syn:anti

72:28

d.r.

(79), 96:4 d.r.

rt

Temp

I (98), 70:30 d.r.

I (49), 70:30 d.r.

Et

114

114, 540

114, 540

114, 540

539

114

539, 113

538, 167

226

C5

R

H

H

Boc

O

Boc

N

N

O

Carbonyl Substrate

B

O

B

O

B

O

B

O

O

O

O

O

O

O

O

OEt

OEt

O

OEt

OEt

B[(–)-Ipc]2

B[(+)-Ipc]2

THF

—

—

THF, rt, 72 h

—

—

Conditions

Boc

I

(50), >95:5 d.r.

R

N Boc

OH

I (68), 96:4 d.r.

I (72), 87:13 d.r.

Me

H

R

0°

rt

96 h

24 h

Temp Time

I (70), 93:7 d.r., 89:11 syn:anti

I (50), 80:20 d.r.

N

OH

d.r.

278, 525

278, 525

525, 541

278, 525

278, 525

Refs.

(85) 86:14

(78) 72:28 525

Product(s) and Yield(s) (%), % ee

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

227

MeO

O

OR

OR

BnO

TrO

O

H

B[(–)-Ipc]2

B[(–)-Ipc]2

O

O

THF, –78°, 7 h

THF, –78°

Neat, rt, 3 d

Neat, rt, 3 d

THF, –78°

THF, –78°

MeO

O

OR

OR

BnO

TrO

TIPSO 4

OH

OH

4

OH

OH

OH

OH

OH 4

O

H

O

B

O

B

O

B[(+)-Ipc]2

B[(–)-Ipc]2

THF, –78°

O

O

H

H

H

H

H

B[(–)-Ipc]2

O

O

O

4

4

O

4

O

O

TIPSO

(72)

MOM

TBDMS

R

MOM

TBDMS

R

d.r.

59:41

60:40

d.r.

78:22

91:1

(39), 85, >99:1 d.r.

(—)

(—)

(—), 93

(68), 90

(65), 90, >20:1 d.r.

544

411

115

115, 113

543

542

330

228

C6

C5

O H

OMe

H O

O

BBN

B

O

B

O

B[(–)-Ipc]2

—

Neat, rt, 3 d

—

—

BnO

H

TBDMSO

TBDMSO

BnO

BnO

TBDMSO

I

Pentane, rt, 2 h

n-C5H11

OH

OH

OH

OH

OH

OMe

OH

I (—), 1:1 d.r.

O

TBDMSO

O

H

H

B[(+)-Ipc]2

THF/ether, –78°

O

TBDMSO

O

O

B[(+)-Ipc]2

THF/ether, –78°

(89), 60:40 d.r.

(—), >99:1 d.r.a

(—), 68:32 d.r.

(49-82)

(49-82)

(—), 97, 15:1 d.r.

Product(s) and Yield(s) (%), % ee

S

H

H

B[(–)-Ipc]2

Conditions

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

S

n-C5H11

BnO

O

TBDMSO

O

TBDMSO

BnO

O

Carbonyl Substrate

103

545

115

341

341

522

522, 532

Refs.

229

O

BnO

O

OBn O

TIPSO

O

H

O H

O

N O

N

CF3

B

O

B

O

B

O

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B(OC6H13-n)2

B

O

O

B(OMe)2

B[(+)-Ipc]2

CF3

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene

Ether, rt

9h

4 Å MS, toluene, –78°,

–120° to –75°

—

O

O

BnO

I

OH

O

O

OH

(78)

OBn OH

OBn OH

TIPSO

OH

I (76), 92

n-C5H11

n-C5H11

OH

97:3 syn:anti

(—), 82:18 d.r.,

99:1 syn:anti

(73), 94:6 d.r.,

(64), >20:1 d.r.

(51), 98:2 d.r.

(56), 95, >99:1 d.r.

549

548, 549

547

31

132

546

250

230

C7

Ph

O H

Carbonyl Substrate

B

TMS

B

O O

O

O

, Pd(PPh3)4

HB

,

toluene, –78°, 4 h

L.A. (10 mol%),

"

Ether, –78° —

O

Ether, –78°

Ether, –78°, 3 h

THF, –78°, 3 h

—

Pentane, rt, 2 h

"

B

O

B(OMe)2

B[(–)-Ipc]2

B[(+)-Ipc]2

BBN

Conditions

I

OH

OH

(72), 88, 99:1 d.r.

(60), 96, >99:1 d.r.

(87)

Product(s) and Yield(s) (%), % ee

(89)

Sc(OTf)3

99:1

99:1 (87)

AlCl3

I (81)

I

d.r. L.A.

I (97), 20:1 d.r.

I (22), 96:4 d.r.

I (40), 96:4 d.r.

I (72), 98, >98:2 d.r.

Ph

Ph

Ph

OH

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

550

25

52

22

43

143

137

250

103

Refs.

231

F

F

F

F

F

O H

O

O

O

O

Cy

B[(–)-Ipc]2

"

O

OPr-i

OPr-i

Cy

B[(+)-Ipc]2

Ph

O B O

B

O

B

O

B

O

THF, –78°, 3 h

–100°

Pentane/ether (1:1),

—

CH2Cl2, –78°, 24 h

Sc(OTf)3 (10 mol%),

–78°, 6 h

(10 mol%), toluene,

Et2AlCl/(S)-BINOL

6h

4 Å MS, THF, –78°,

12 h

Petroleum ether, rt,

F

F

F

OH

F

F

F

F

F

OH

I (75), 94, >19:1 d.r.

F

F

I (53), 59, >49:1 d.r.

I

OH

I (90), 55, 98:2 d.r.

I (62)

I

(75), 94, >95:5 d.r.

(77), 97, >99:1 d.r.

(19), 8, 99:1 d.r.

491

249

250

27, 28

25

37

64

232

C7

R

OR

OR

O H

O H

O H

R = H, MeO

R = H, MeO, O2N

O2N

Carbonyl Substrate

O

B

O

B

O

O

O

O

O

BF3–K+

"

BF3–K+

B

O

O

CF3

N O

N

O

OPr-i

OPr-i

O

OPr-i

OPr-i

CF3

I d.r.

9h

4 Å MS, toluene, –78°,

6h

4 Å MS, toluene, –78°,

15 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

I

OH

MeO

H

(98)

(96)

(95)

(90), 83, 98:2 d.r.

>98:2

>98:2

d.r.

>98:2

(94)

O2N R

96:4

>98:2

(93)

(92)

MeO

H

I (80), 92

I

I

O2N

(91)

MeO

R

TBDMS

Me

R

CH2Cl2, –78°, 15 min R

OH

OH

(91)

OR

OR

H R

O2N

Product(s) and Yield(s) (%), % ee

BF3•OEt2 (2 equiv),

CH2Cl2, –78° to rt

Conditions

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

>98:2

96:4

>98:2

d.r.

(99)

(100)

132

519, 37

100

99

98, 99

551

Refs.

233

O

TBDPSO

i-Pr

i-Pr

MeO

PMBO

TBDPSO

O

p-MeOC6H4

t-Bu

O

O

O

H

H

H

O

O

H

H

O

H

H

TBDMS O

OH

O

O

B

O O

O

O

OPr-i

OPr-i

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B(OPr-i)2

B[(–)-Ipc]2

B

O

4 Å MS, toluene, –78°

THF, –78°, 4 h

THF, –78°, 4 h

THF, –78°, 6 h

THF, –78°, 6 h

Toluene, –23°

THF, ether, –78°, 2 h

CDCl3, 4 kbar, rt

OH

O

TBDPSO

i-Pr

i-Pr OH

OH

I (—), 1:1 d.r.

MeO

PMBO

TBDPSO

O

p-MeOC6H4

t-Bu

O

OH

(60)

(—), 6:1 d.r.

(78), 1.6:1 d.r.

OH (85), 5:1 d.r.

(62)

(56)

TBDMS OH

OH

OH

(50), 60:40 d.r.

364, 441

554

554

354

354

553

552

521

234

C8

C7

O

Ph

O

n-C7H15

MeO

H

O H

OMe

O

H

Carbonyl Substrate

O

THF, –78° to rt, 2 h —

"

THF, –78°, 18 h

CH2Cl2, H2O, rt, 15 min

n-Bu4NI (10 mol%),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

CH2Cl2, –78°, 15 min

BF3•OEt2 (2 equiv),

"

B[(+)-Ipc]2

"

"

BF3–K+

BF3•OEt2 THF, –78° to rt, 3.5 h

"

–78° to rt

BF3•OEt2, THF,

THF, –78° to rt

6h

4 Å MS, toluene, –78°,

"

"

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

O

Conditions

O

I

OH

OMe

(90), 95:5 d.r.

(99)

I

OH

I (85-90), >95

I (80)

Ph

I (94), >98:2 d.r.

I (76), >98:2 d.r.

558

557

556

100

99

98, 99

420

I (74), >98:2 d.r.

421

422

420

555

I (90), 95:5 d.r.

(75), >95, >95:5 d.r.

OH

Refs.

I (90)

I (72), 95:5 d.r.

n-C7H15

MeO

Product(s) and Yield(s) (%), % ee

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

235

Ph

O

BnO 4

PMBO

TBDMSO

Ph

O

O

O

H

H

O

O

B[(–)-Ipc]2

B[(+)-Ipc]2

"

BF3–K+

B

O

B

O

BBN

THF, –78°

THF, –78°

CH2Cl2, rt, 6 h

BF3•OEt2 (5 mol%),

CH2Cl2/H2O, rt, 30 min

n-Bu4NI (10 mol%),

–40°, 4 h

La(OPr-i)3, CuF, DMF,

(R,R)-i-Pr-DuPHOS,

–40°, 5 h

La(OPr-i)3, CuF, DMF,

(R,R)-i-Pr-DuPHOS,

Pentane, rt, 2 h

Ph

HO

OH

OH

4

BnO 4

PMBO

BnO

PMBO

I

OH (—), 2:1 d.r.

(—)

(97), 90:10 d.r.

(90), 92, 62:38 d.r.

(94), 87, 84:16 d.r.

(97)

OH

I (85), 90:10 d.r.

TBDMSO

Ph

HO

Ph

543

543

99

276

164

164

103

236

C9

C8

Ph

H

OBn O

O

O

Ph

H

O H

OBn OBn

4

O

n-C5H11

HO2C

n-Pr

PMBO

BnO

PMBO

H

Carbonyl Substrate

O

O

O

BF3–K+

Ph

O B O

B(OPr-i)2

B

O

B

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B[(+)-Ipc]2

15 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

CH2Cl2, –78°, 24 h

Sc(OTf)3 (10 mol%),

–10° to rt

Et3N, CH2Cl2,

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

THF, –78°

THF, –78°

Conditions

PMBO

BnO

Ph

n-C5H11

HO2C

OH

HO Ph

OH

(—), >99:1 d.r.

(—)

(—), 2:1 d.r.

(99), >98:2 d.r.

(61), 95, >49:1 d.r.

(95), 99:1 d.r.

OBn OH

OH

OH

OBn OBn I

4

I (—), 1.5:1 d.r.

n-Pr

4

PMBO

BnO

PMBO

Product(s) and Yield(s) (%), % ee

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

100

28

106

559

559

543

543

Refs.

237

Br

i-Pr

i-Pr

Ph

Ph

O

7

O

H

O

H

H

O

O

H

H

B

O

B

O

B

O

B

O

B

O

O

O

O

O

O

O

O

O

O

Ph

O B O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Toluene, –78°

Toluene, –78°

2h

4 Å MS, toluene, –78°,

2h

4 Å MS, toluene, –78°,

Neat, rt, 4 d

CH2Cl2, –78°, 24 h

L.A. (10 mol%),

Br

Br

i-Pr

i-Pr

Ph

Ph

7

OH

7

OH

OH

OH — — —

(48), — (<10), — (65), —

TfOH TFA

OH

(91), 76

(91), 74

(70), 96:4 d.r.

(70), 96.4:3.6 d.r.

(92), 77:23 d.r.

OH

d.r. >49:1

TiCl4

Sc(OTf)3 (52), 96

L.A.

560

560

526

526

521

27, 28

238

C10

C9

n-C7H15

n-C7H15

n-C6H13

Ph

TBDMSO

O

O

O

H

H

H

H

O

Carbonyl Substrate

B

O

B

O

"

B

O

"

O

O

O

O

O

O

BF3–K+

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

6h

4 Å MS, toluene, –78°,

toluene, –78°

n-C7H15

n-C7H15

OH

OH

(83), 62, 97:3 d.r.

(85-95), 86, 97:3 d.r.

(55-70), 88

Cr(CO)3, 4 Å MS,

(55-70), 83

Temp

(55-70), 61

–90°

OH

OH

(96), 75:25 d.r.

–78°

OH

(84), 75:25 d.r.

toluene

n-C6H13

n-C6H13

Ph

TBDMSO

Ph

OH

Product(s) and Yield(s) (%), % ee TBDMSO

Cr(CO)3, 4 Å MS,

4 Å MS, toluene, –78°

30 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

Conditions

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

519, 37

128

130

130

276

99

Refs.

239

O

SEMO

MeO

TBDPSO

MeO

TBDMSO

MeO

Ph

Ph

O

n-C9H19

O

O

O

H

H

O H

O

O

O

H

H

H

O

B

O O

O

O

OPr-i

OPr-i

B[(–)-Ipc]2

B[(–)-Ipc]2

O

OPr-i

OPr-i

B[(+)-Ipc]2

B(Bu-n)2

"

B

O

O

91 h

4 Å MS, toluene, –78°,

Ether, –78°, 1.5 h

THF, –78°

—

Neat, 0-5°

6h

4 Å MS, toluene, –95°,

6h

4 Å MS, toluene, –78°,

MeO

O

O

SEMO

MeO

TBDPSO

MeO

TBDMSO

Ph

Ph

I (69), 86

n-C9H19 I

O

OH

OH

H OH

OH

OH

OH

(77)

561

238

519

519, 37

564

(51), 6.2:1 d.r. 563, 430

(90), 19:1 d.r. 562

(98), 2.4:1 d.r.

(78)

(80), 82, 99:1 d.r.

240

C11

C10

O

n-Pr

BnO

O

H

O H

OBn

O O

O H

O

H

H

OBn O

H

OTBDMS

O

MOMO

TIPSO

MOMO

O

3

H

O

Carbonyl Substrate

H

O

B

O

B

O

B

O

B

O

O

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Toluene, –80° to –70°

THF, –78°

Conditions

O

O

H

I

O

H

OBn

O

H

OH

OBn OH

O

H

OTBDMS

I (—), 1:1 d.r.

n-Pr

BnO

O

MOMO

TIPSO

MOMO

O

OH

3

(52)

(79)

(59), >95

(—), 1:1.3 d.r.

OH

Product(s) and Yield(s) (%), % ee

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

559

559

570

568, 569,

566, 567,

566

565

Refs.

241

C14

C13

O

TIPSO

OBn

Ph

H

OBn

Ph

O

OH

O

H

n-Bu

AcS

Br

Ph

Ph

n-Pr

BnO

OTIPS

OBn O

O

O

H

OMe

H

H

O

O

O

O O O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B(OPr-i)2

BBN

B

O

B

O

O

–78°

4 Å MS, toluene, –78°

–10° to 40°, 32 h

Et3N, CH2Cl2,

Pentane, rt, 2 h

4 Å MS, toluene, –78°

4 Å MS, toluene, –78° H I

O H

OBn

OH

n-Bu

TIPSO

OBn

OH

HO Ph

AcS

Br

Ph

Ph

Ph

(—), >99:1 d.r.

OTIPS

OH

OMe

OH

109

103

559

559

(61), >97.5:2.5 d.r. 572

(80), 20:1 d.r. 571

(80), >99:1 d.r., 5:95 syn:anti

(96)

OBn OH

I (—), >99:1 d.r.

n-Pr

BnO

242

C16

C14

a

O

O

CO2Me

O

NH

O

H

OTIPS

O

O

H

H

O O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

O

B[(+)-Ipc]2

B[(+)-Ipc]2

THF, –78°, 2 h

–90° to rt, 18 h

4 Å MS, toluene,

THF, –78°, 2 h; rt

–78°

Conditions

I

O

OH

OTIPS

CO2Me

O

NH

O

I (60), >95:5 d.r.

TBDMSO

RO

PhO2S

n-Bu

TIPSO

(67), 3:1 d.r.

573, 574

572

Refs.

575, 576

(80), 67:33 d.r. 575, 576

(67), 7:1 d.r. TES

(65), 11:1 d.r.

H

R

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 2. ADDITION OF Z-CROTYL REAGENTS (Continued) Allylborane Reagent

The reference reports uncertainty over the stereochemical assignment of the product.

TBDMSO

RO

PhO2S

n-Bu

TIPSO

Carbonyl Substrate

243

C2

Boc

O

H N

H

O H

Carbonyl Substrate

B

TMS

B[(+)-Ipc]2

B(Bu-n)3–Li+

B O

Ether, –78°, 3 h

B(4-d-Icr)2

O

THF, –78°, 3 h

B[(–)-Ipc]2

—

, – Li+ B(Bu-n)3, ether, –70°

Ether, –78° to rt

Ether, –78°, 3 h

Ether, –78°, 3 h

THF, –78°, 3 h

B(2-d-Icr)2

B[(+)-Ipc]2

Conditions

(76), 96, 99:1 d.r.

Product(s) and Yield(s) (%), % ee

(78), 95, 99:1 d.r.

Boc

H N

OH (—), 97

I (—), 80:20-92.5:7.5 d.r.

I (40), 93:7 d.r.

I (73), 97, >98:2 d.r.

I (—), 94, >99:1 d.r.

I

OH

I (75), 96, >99:1 d.r.

I

OH

TABLE 3. ADDITION OF E-CROTYL REAGENTS Allylborane Reagent

517

577

22

143

497

44, 497

497

44, 497

Refs.

244

C3

C2

RO

O H

R = TBDMS

R = Bn

R = TIPS

R = PMB

H R = TBDPS

O

Carbonyl Substrate

O

O O

O

O

O

Ph

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

Ph

O B O

B

B

O

B

O

B[(–)-Ipc]2

Allylborane Reagent

THF, –78°, 3 h

CH2Cl2, –78°, 24 h

Sc(OTf)3 (10 mol%),

Ether, rt

Toluene, –78°

4 Å MS, toluene, –78°

THF, ether, –78°

Conditions

RO

OH

OH (74), 95, >49:1 d.r.

(61), 92, >99:1 d.r.

(65), 90, 99:1 d.r.

I (86), 52, >95:5 d.r.

I (80), 92, 20:1 d.r.

I

OH

Product(s) and Yield(s) (%), % ee

I (79)

RO

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

137

27, 28

581

330

559

580

578, 579,

Refs.

245

O H

B(Bu-n)3–Li+

, – Li+ B(Bu-n)3, ether, –70°

Ether, –78°

O O

Ether, –78° to rt

B(OMe)2

B

I (—), 94, >99:1 d.r.

I (—), 80:20-92.5:7.5 d.r.

I (62), 97:3 d.r.

I (61), 97:3 d.r.

I (75), 94, >99:1 d.r.

Ether, –78°, 3 h

577

22

43

497

137

506

THF, –78°, 3 h

137, 497

I (70), 95-96, 98:2 d.r.

142

I (70), 90, 99:1 d.r.

B(4-d-Icr)2

THF/ether, –78°, 3 h

I

(81), 96, 93:7 d.r.

506

OH

137, 497

497

I (70), 95-96, 98:2 d.r.

(76), 98, >99:1 d.r.

I (78), 92, 99:1 d.r.

I

OH

"

Ether, –78°, 3 h

B[(–)-Ipc]2 "

THF, –78°, 4 h

THF, ether, –78°, 3 h

B

THF, –78°, 3 h

B[(+)-Ipc]2

Ether, –78°, 3 h

"

B(2-d-Icr)2

246

C3

R

O H

Boc

H

R = Boc

R = Ac

R = Boc

HN

HN

O

Carbonyl Substrate

B

O

B

O

B

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Conditions

–78°, 15 h

4 Å MS, toluene,

acetone, –78°

4 Å MS, toluene,

–78°, 15 h

4 Å MS, toluene,

–78°, 15 h

4 Å MS, toluene,

–78°, 4 h

"

B[(–)-Ipc]2

—

—

B[(–)-Ipc]2

B[(+)-Ipc]2

Allylborane Reagent

Boc

Boc

OH

R

OH

R

I

I (68), 75:25 d.r.

I (67), 87:13 d.r.

HN

HN

OH

I

(53), 75:25

(85), >95:5 d.r.

(—), >97:3 d.r.

(—), >97:3 d.r.

Product(s) and Yield(s) (%), % ee OH

I (81)

HN

HN

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

278

584, 278

278

278

583

520, 582

520

Refs.

247

H

H

O

R = PMB

R = TBDMS

RO

NBn2

O

NBn2

O

H

O

O

O

O OH

R

—

THF, –78°

Ether, THF, –78°,

"

B[(+)-Ipc]2

"

3h

I (67), >99, >99:1 d.r.

–78°

"

I (76), 91

RO

RO

I (48)

I

OH

OH

I (71), >85, >50:1 d.r.

2h

I

OH

(62), 92

(70)

(55)

(92), 9:1 d.r.

(94), >95:5 d.r.

(68), >95:5 d.r.

–78° to rt

RO

NBn2

OH

NBn2

HN

OH

"

THF, –78° to –30°

Neat, rt, 4 d

acetone, –78°

4 Å MS, toluene,

–78°, 15 h

4 Å MS, toluene,

"

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B

O

B

O

O

588, 589

413, 339

341

587

586

585

406

521

278

278

248

C3 H

H

R = Bn

O

R = TBDPS

R = TBDMS

OR

RO

O

Carbonyl Substrate

O

B[(+)-Ipc]2

Ph

O B O

B O

OPr-i

OPr-i

THF, –78° , 3 h

CH2Cl2, –78°, 24 h

Sc(OTf)3 (10 mol%),

–78°, 4 h

4 Å MS, toluene,

THF, –78° to rt, 4 h

B[(+)-Ipc]2

O

THF, –78°, 2 h

"

O

THF, –78°

THF, –78°

Conditions

"

B[(–)-Ipc]2

Allylborane Reagent

I

OH

OR

RO

RO

RO

OH

I (68)

OH

I

OH

OH

(85), 97:3 d.r.

(63), 94, >49:1 d.r.

(71), 85, >98:2 d.r.

(70), >95, >20:1 d.r.

(72), 95, 20:1 d.r.

Product(s) and Yield(s) (%), % ee

I (81), 95, 20:1 d.r.

RO

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

167, 538

27, 28

519, 37

595

594

592, 593

590, 591

Refs.

249

TES

TMS

HO

O

TBDMSO

H

H

H

O

O

O

B[(+)-Ipc]2

B[(–)-Ipc]2

B(OPr-i)2

"

BF3–K+

THF, –78°

THF, –78°

–10° to rt, 15 h

Et3N, CH2Cl2,

30 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

CH2Cl2, rt, 6 h

BF3•OEt2 (5 mol%),

Neat, rt, 4 d

O

R = Bn O

Ether, –78°

B[(–)-Ipc]2

R = PMB

B

THF, –78°, 3 h

B[(–)-Ipc]2 I

I

HO

TES

TMS

HO

OH

OH

I (95), 75:25 d.r.

TBDMSO

OH

I (46), 77:23 d.r.

I (64)

OR

OH

(67)

(66), 90

(72), 97:3 d.r.

(72), 75:25 d.r.

(80), 95:5 d.r.

573

266

109

276

99

521

597

167, 538

250

C3

O

EtO2C

HO2C

RO

O

O

O

Carbonyl Substrate

O

O

O

Ph

BF3–K+

B

O

B

O

B(OPr-i)2

BBN

O

OPr-i

OPr-i

Ph

Allylborane Reagent

–78°, 2 h

BF3•OEt, CH2Cl2,

6h

4 Å MS, –78° to rt,

–78° to rt, 6 h

4 Å MS, toluene,

–10° to rt

Et3N, CH2Cl2,

30 min

Ether, –76° to 0°,

Conditions

75:25 65:35 70:30 100:0

(79) (88) (80) (90)

2,6-Me2C6H3 3,5-Me2C6H3 2,3,6-Me3C6H2 2,6-(t-Bu)2-3-MeC6H2

5:1 2:1

(80), 62 (83), 33

3.2:1

7:1

d.r.

CH2Cl2

(82), 53

(84), 73

(86), 6, 53:47 d.r.

ether

THF

toluene

Solvent

I (92), >98:2 d.r.

I

EtO2C

HO

I

80:20

(89)

Ph

(95), 99:1 d.r.

80:20

(94)

PhCH2

HO

85:15

(90)

t-BuCH2

d.r. 73:27

(96)

OH

Product(s) and Yield(s) (%), % ee

Me

O R

HO2C

RO

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

98

134

134

106

598

Refs.

251

O

O

O H

"

B

O

B

O

B[(–)-Ipc]2

B

B

CH2Cl2, 24 h

24-48 h

CH2Cl2, –78° to rt,

THF, –78°, 4 h

I (—)

O

O

O

O

I

Anti:Syn 94:6 95:5 97:3 >99:1

d.r. 52:42 51:44 51:46 53:47

Temp –78° to rt rt –20° –78°

(75-85), 52:42 d.r., 94:6 anti:syn

OH

(74), 6.9:1 d.r., 98:2 anti:syn

OH

I (72), >20:1 d.r.

(71), 34:1 d.r., 99:1 anti:syn

I

—

O

I (62), 2:1 d.r., 89:11 anti:syn

O

THF, –78°, 4 h

THF, –78°, 4 h

OH

118

537, 118

142

599

142

142

252

C3

O

O

O H

Carbonyl Substrate

O

CF3

CF3

(37)

B

B

O

B

O

B

O

O O

O

O

O

O

O

O N

Ph

CF3

N O

N

O

OPr-i

OPr-i

O

N

CF3

–78° to rt, 18 h

Petroleum ether,

9h

4 Å MS, toluene, –78°,

4 Å MS, toluene, –78°

7h

4 Å MS, toluene, –78°,

–78° to rt, 18 h

(87), 91:9 d.r., 96:4 anti:syn

O

I (—), 72:28 d.r.

I (77), 95:5 d.r.

O

OH

I (84), >99:1 d.r.

I (65)

I

4 Å MS, toluene,

O

"

O

I (85), 98:2 d.r., 98:2 anti:syn

O

—

OH

Product(s) and Yield(s) (%), % ee

4 Å MS, toluene, –78°

O

OPr-i

OPr-i

Conditions

"

B

O

Allylborane Reagent

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

288

132

602, 170

126, 548,

132

603

170

601, 602,

600

Refs.

253

C4

O

O

O

O

O

H

O

O

O

O

H

O

H

O

H

H

racemic

O

O

O

O

O

O

O

O

B[(–)-Ipc]2

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Ph

B[(–)-Ipc]2

B

O

B

O

B

O

B

Ether, THF, –78°, 3 h

Ether, –78°, 2 h

1.5 h

4 Å MS, toluene, –78°,

4 Å MS, toluene, –78°

1.5 h

4 Å MS, toluene, –78°,

–78° to rt, 18 h

Petroleum ether,

O

O

O (77), 88:12 d.r.

OH

O

OH

(—), 84, 9:1 d.r.

(58), 99, 14:1 d.r.

(84), 91:9 d.r.

(85), 98:2 d.r., 98:2 anti:syn

OH

O

OH

O

OH

I (—), 2:1 d.r.

605, 606

604

524

549

524

288

254

C4

BnO

i-Pr

Cl

O

O

H

H

O H

Carbonyl Substrate

B

O

B

O

B

O

O

O

O

O

OPr-i

OPr-i

B(Bu-n)3–Li+

B

O

TMS

B[(–)-Ipc]2

B

Allylborane Reagent

4 Å MS, toluene, –78°

Neat, rt, 4 d

– Li+ B(Bu-n)3, ether, –70°

Ether, –78°

Ether, –78°, 3 h

Ether, –78°, 3 h

THF, –78°, 4 h

Conditions

I

OH

I

OH (59), 96:4 d.r.

(94), 96, >98:2 d.r.

BnO

Cl

OH

OH (87), 80

(71), 53:47 d.r.

I (—), 80:20-92.5:7.5 d.r.

i-Pr

i-Pr

OH

(76), 97, 96:4 d.r.

Product(s) and Yield(s) (%), % ee

I (80), 88:12 d.r.

i-Pr

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

609

521

577

22

143

608

305, 607,

142

Refs.

255

RO

O

Toluene, rt

O

R = TBDMS, TBDPS, Bn B

Ether/THF, –100°

B[(–)-Ipc]2

R = TBDPS

THF, –78°, 3 h I

I (—), >99:1 anti:syn

I (74)

RO

(87), 98:2 d.r.

d.r. 62:38 68:32

Bn

61:39 TBDPS

TBDMS

R

B[(–)-Ipc]2

R = Bn

OH

I (74)

THF/ether, –85°,

B[(+)-Ipc]2

R = TBDPS

169, 297

527

167

530

513

20 h

167

R = TES I (68), >98:2 d.r.

611

167, 610,

I (76), >98:2 d.r.

I

(48), 95:5 d.r.

THF, –78°

RO

OH

THF/ether, –78°

THF, –78°, 4 h

"

H

B[(+)-Ipc]2

B[(+)-Ipc]2

R = Bn

O

256

C4

RO

H

R = TBDPS, TBDMS

R = TBDPS, TBDMS

R = TBDMS, TBDPS, Bn

O

Carbonyl Substrate

B

O

B

O

B

O

B

O

B

O

O

O

O

O

O

O

O

O

O

O

CF3

N O

N

CF3

N O

N

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

CF3

CF3

Allylborane Reagent

–55° to 0°

4 Å MS, toluene,

–55° to 0°

4 Å MS, toluene,

–78°, 18 h

4 Å MS, toluene,

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Conditions

RO

I

RO

RO

RO

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

10 h

TBDMS

10 h

12 h

TBDPS TBDMS

Time

R

OH

12 h

Time TBDPS

R

(81), —

97:3 99:1 99:1

(78)

90:10

96:4

d.r.

>97:3

(85)

(80)

95:5

(87)

d.r.

>97:3 d.r.

— TBDMS

>99:1 98:2 98:2

Anti:Syn

d.r.

I

81:16 88:11 85:14

d.r.

97:3 82:16 93:5

Anti:Syn

TBDPS

(77), 60

(—) (85) (—)

(80) (—) (—)

d.r.

R

TBDMS TBDPS Bn OH

R

TBDMS TBDPS Bn OH

R

OH

Product(s) and Yield(s) (%), % ee

132

132

596

615

297, 169,

613, 614

169, 612,

297, 456,

Refs.

257

RO

R = TBDMS, t-Bu

R = TBDMS

R = t-Bu

R = PMB

B

O

B

O

B

O

B

O

O

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4h

4 Å MS, toluene, –78°,

8h

4 Å MS, toluene, –78°,

THF, –78°, 3 h

B[(–)-Ipc]2

R = Bn

O

THF, –90°, 16 h

THF, –78°, 3 h

B[(+)-Ipc]2

H

B[(+)-Ipc]2

R = TIPS

R = Bn

O

I

I

I

RO

— 4h

t-Bu

Time TBDMS

R

I

OH

I (71), 82:18 d.r.

I (78), 85:15 d.r.

RO

OH

I (50), 93:7 d.r.

RO

OH

(74)

(—)

18:1

9:1

d.r.

(86), 89:11 d.r.

(—), 94:6 d.r.

(—), 98:2 d.r.

271

364

615

619, 266,

618

195, 617

167

616

167

258

C4 O

O

O

O

O

TBDPSO

BnO

O

O

TBDMSO

BnO

H

H

O

O

O

H

H

H

OMe O

O

O

H

Carbonyl Substrate

O

B

O

B

O

B

O

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B

O

Allylborane Reagent

Toluene, –78°

1h

4 Å MS, toluene, –78°,

4 Å MS, toluene, –78°

THF, –78°, 4 h

THF, –78°, 4 h

THF, –78°, 3 h

—

Conditions

O

O

O

O

O

TBDPSO

TBDPSO

BnO

O

O

OH

OH

OH

(82)

(95), 9:1 d.r.

(88), 95:5 d.r.

(88), 95:5 d.r.

(63), 87:13 d.r.

(75), >97.5:2.5 d.r.

OMe OH

(73), >97.5:2.5 d.r.

OMe OH

OH

OH

Product(s) and Yield(s) (%), % ee

TBDMSO

BnO

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

622

621

620

536

536

250

52

Refs.

259

O

O

O

HO2C

Boc

H N

O

O

O

H

H

H

Et

OTBDMS

O

O

O

O

O

O

O

O

O

O

O

O

O

B(OPr-i)2

B

O

B

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

B

O

–10° to rt

Et3N, CH2Cl2,

Toluene, 20°

Toluene, 0°

THF, ether, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

24-48 h

CH2Cl2, –78° to rt,

O

O

OH

HO2C

HO Et

O

O (80), 7:1 d.r.

(68), 90, >99:1 d.r.

93:7 anti:syn

(88), 93:4 d.r.,

92:8 anti:syn

(80), 96:4 d.r.,

98:2 anti:syn

(75-85), 52:48 d.r.,

(93), 99:1 d.r.

OTBDMS

OH

I

OH

OH

OH

I (—), 16, 99:1 d.r.

Boc

H N

O

O

O

O

O

O

106

624

623

623

126

126

537, 118

260

C5

Et

t-Bu

O

O

H

H

Carbonyl Substrate

B

O

O

I

(65), >90, >3:1 d.r.

Ether, –70°, 3 h

B[(+)-Ipc]2

OH

I (65), 92, 78:22 d.r., 85:15 anti:syn

Ether, –78°, 3 h

Et

I (75), 96:4 d.r.

Ether, –78°

"

(75), 96:4 d.r.

(41), 73, 95:5 d.r.

(69), 99, >98:2 d.r.

"

I

OH

I (95), >98:2 d.r.

t-Bu

OH

OH

(72), 95, 96:4 d.r.

Et

15 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

6d

4 Å MS, toluene, –78°,

t-Bu

t-Bu

OH

Product(s) and Yield(s) (%), % ee

THF, –78°, 3 h

O

OPr-i

OPr-i

Ether, –78°, 3 h

THF, –78°, 4 h

Conditions

B[(–)-Ipc]2

BF3–K+

B

O

TMS

B

Allylborane Reagent

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

306

607

538

167

100

519, 37

143

142

Refs.

261

Et

O H

racemic

racemic

O

O

O

O

O

O

Ph

Ph

Ph

B

B

O

O

O

O

Ph

Ph

B[(+)-Ipc]2

B

B

B

O

–78° to rt

Petroleum ether,

–78° to rt

Petroleum ether,

Ether, –78°, 3 h

–78° to rt

Petroleum ether,

–78° to rt

Petroleum ether,

–78° to rt

Petroleum ether,

I

(46), 77:23 d.r.

(70), 91:9 d.r.

I

OH

OH

I (96), 76:24 d.r.

Et

Et

>99:1 anti:syn

(98), 75:25 d.r.,

(65), 54, 78:22 d.r.

I (—), 76:24 d.r., >99:1 anti:syn

I (99), 92:8 d.r., >99:1 anti:syn

I (95), 76:24 d.r., >99:1 anti:syn

Et

Neat, rt, 4 d

O B

OH

I I (70), 91:9 d.r.

Ether, –78°

"

OH Et

THF, –78°, 3 h

B[(+)-Ipc]2

114

114, 540

607

540

114, 540

114

113

539, 115,

538

167

262

C5

H

H

O

O

OR

OR H

H

H

R = DMPM

O

TBDMSO

4

O

Boc

OR

BnO

BnO

N

O

O H

Carbonyl Substrate

O

B

O

B

O

B

O

O

O

O

O

O

OPr-i

OPr-i

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B

O

Allylborane Reagent

4 Å MS, toluene, –78°

Neat, rt, 3 d

Neat, rt, 3 d

—

—

THF, –78°

THF, rt, 60 h

Conditions

4

OH

Boc

OR

OR

OH

OH

OH

TBDMSO

TBDMSO

OR

BnO

BnO

BnO

N

MOM

TBDMS

R

MOM

TBDMS

R

(49-82)

(49-82)

(85), >98:2 d.r.

(—)

(—)

OH

OH

(—), 75

74:26 anti:syn

(81), 95:5 d.r.,

94:6

98:2

d.r.

89:11

98:2

d.r.

Product(s) and Yield(s) (%), % ee OH

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

625, 626

115

115, 113

341

341

543

525

Refs.

263

C6

O

n-C5H11

O

O

PMBO

TBDMSO

R = TES

H

S

H

O

O

H

H O

O

O

O

O

O

N Ts

0.4 M

B

O

B

O

B

Ts N

CF3

N O

N

O

OPr-i

OPr-i

Ph

Ph

B[(+)-Ipc]2

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

O

CF3

6h

4 Å MS, toluene, –78°,

4h

4 Å MS, toluene, –78°

THF, –78°

—

—

Neat, rt, 3 d

4h

4 Å MS, toluene, –78°,

O

I

OH

S

H

I (83), 92

n-C5H11 I

OH

I (74-82), 91-95

n-C5H11

O

PMBO

TBDMSO

I (70), >98:2 d.r.

OH

OH

(84), 86, 99:1 d.r.

(67), 95, >99:1 d.r.

(58)

(—), 90:10 d.r.

132

519, 37

50

250

627

115

617

264

C6

AcN

O

TBDPSO

Et

O

O

H

H

Fe(CO)3 H

H

TBDMSO

O

O

O H

Carbonyl Substrate

B

O

B

O

B

O

B

O

O

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Allylborane Reagent

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

0° to rt, 14 h

Petroleum ether,

4 Å MS, toluene, –78°

Conditions

(90), >98, >50:1 d.r.

AcN

O

TBDPSO

OH (76), 80:20 d.r.

(87), 94:6 d.r.

OH

(99), 95:5 d.r., >99:1 anti:syn

Et

OH

OH

Product(s) and Yield(s) (%), % ee

Fe(CO)3

TBDMSO

H

O

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

584, 278

629, 630

197

149, 628,

342, 190

Refs.

265

N

BnO

BnO

O

O

PMBO

TBDMSO

TESO

O

O

H

O

H

H B

O

B

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

–78° to rt, 18 h

4 Å MS, toluene,

2h

4 Å MS, toluene, –78°,

THF, –78°

THF, –78°

Ether, –78°

–78°, 4 h

N

BnO

BnO

O

OH

PMBO

TBDMSO

TESO

O

OH

OH

OH (76), 80:20 d.r.

(75), 4:1 d.r.

(—), 3.5:1 d.r.

(62), 95:5 d.r.

(60), 98, 10:1 d.r.

(83), 6:1 d.r.

(80)

OH

OH

OBn OH

Boc

O

TBDMSO

O

AcN

PMBO B[(–)-Ipc]2

B[(+)-Ipc]2

O

4 Å MS, toluene, –78°

PMBO H

O

B[(+)-Ipc]2

B

OPr-i

OPr-i

PMBO

H

H

H

O

O

PMBO

O

O

O

OBn O

Boc

TBDMSO

O

AcN

O

633

632

631

413

597

583

278

266

C7

C6

O

O

N

O

O

O

O

H

H

OBn O

OAc O

H

H

Carbonyl Substrate

O

O

O

O

OCOPh,

—

THF, –78°, 3 h

B[(–)-Ipc]2

40°, 2 h

THF, rt, 24 h;

BEt3, Pd(PPh3)4,

OCOPh,

THF, rt, 24 h

BEt3, Pd(PPh3)4,

3h

THF, ether, –78°,

4 Å MS, toluene, –78°

–78° to rt, 18 h

4 Å MS, toluene,

Conditions

B[(+)-Ipc]2

"

BEt2

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

Allylborane Reagent

OBn OH

(60)

N

I

OH

OH

I

OH

I (59), 96, >99:1 d.r.

(79), 88, 99:1 d.r.

(64), 2.6:1 d.r.

(31), 83, >96:4 d.r.

O (—), 86:14 d.r., 97:3 anti:syn

O

OAc OH

Product(s) and Yield(s) (%), % ee

I (60), 2.2:1 d.r.

O

O

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

137

250

483

483

634

549

603

Refs.

267

B

TMS

B

O

"

"

O

O OEt

O

OEt

L.A. (10 mol%),

"

O

2

OAc,

O

OEt

OEt

toluene, 20°, 21 h

Pd2(dba)3, DMSO,

O B

O

toluene, –78°, 6 h

(10 mol%),

Et2AlCl/(S)-BINOL

toluene, –78°, 4 h

(10 mol%),

AlCl3/(S)-BINOL

toluene, –78°, 4 h

—

"

O

Ether, –78°

O B

Ether, –75°

B(OMe)2

Ether, –78°, 3 h

I

OH

Sc(OTf)3

AlCl3

L.A.

I (76), 33

I (40), 51, 99:1

I

I (97), 10:1 d.r.

I (80), 94:6 d.r.

I (50), 99:1 d.r.

(94)

(92)

I (82), 97, >98:2 d.r.

d.r.

(92), 39, >99:1

>99:1

>99:1

349

25

25

25

52

22

43

143

268

C7

R

O

H

H

R = H, MeO, O2N

R = BocO

O

Carbonyl Substrate

O O

N Ts

BF3–K+

B[(–)-Ipc]2

Ph

O

OPr-i

OPr-i

Ph

BR3–Li+

B

Ts N

"

B

O

O B O Ph

Allylborane Reagent

CH2Cl2, –78°, 15 min

BF3•OEt2 (2 equiv),

4.5 h

THF, ether, –78°,

, – Li+ BR3, ether, –70°

CH2Cl2, –78°

toluene, –78°

Co(CO)3, 4 Å MS,

3h

4 Å MS, THF, –78°,

CH2Cl2, –78°, 24 h

Sc(OTf)3 (10 mol%),

Conditions

I

OH

OH

I

R

I

(94) (91) (96)

H MeO O2N

R

I

OH

d.r.

>98:2

97:3

>98:2

(82), >99:1 d.r.

90:10-91.5:8.5

(—) n-Bu

d.r. 90:10-91.5:8.5

(—) Et

R

I (74-82), 91-95

(91), 67, >99:1 d.r.

(60), 97, >49:1 d.r.

Product(s) and Yield(s) (%), % ee

I (90), 92, 98:2 d.r.

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

98, 99

635

577

50

128

519, 37

27, 28

Refs.

269

F

F

F

F

F

O H

O

"

O

OEt

OEt

B[(+)-Ipc]2

O B

O

O

O

R = O2N B

BF3–K+

R = H, MeO

"

O OAc,

2

O 2

OAc,

O

OEt

OEt

—

–100°

Pentane/ether,

toluene, 20°, 21 h

Pd2(dba)3, DMSO,

O B

O

60°, 21 h

Pd2(dba)3, DMSO,

O B

15 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

(95) (98)

H MeO

F

F

F

OH

I I (84), 97, >99:1 d.r.

F

F

O2N

OH (67), 50

(72), 92, >19:1 d.r.

>98:2

>98:2

d.r.

>98:2

(94)

O2N R

97:3

(95)

MeO

d.r. >98:2

(93)

H

R

I (81), >99:1 d.r.

I

I

250

249

349

636, 349

100

99

270

C7

F

F

F

F

O H

F

O H

Carbonyl Substrate

O

O

B

O

O

N Ts

Ts N

0.4 M

B

O

"

"

B

O

Ph

Ph

CF3

N O

N

O

OPr-i

OPr-i

B[(+)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

CF3

THF, –78°

6h

4 Å MS, toluene, –78°,

3h

4 Å MS, toluene, –78°,

1h

4 Å MS, toluene, rt,

3h

4 Å MS, toluene, –95°,

THF, –85°, 18 h

THF, –78°, 3 h

Conditions

F

F

I

OH

OH

F

OH

(87), 77 (88), 70 (87), 62

toluene ether THF CH2Cl2

OH (74-82), 91-95

>99:1

>99:1

>99:1

d.r. 96:4

(85), 87

Solvent

I (85), 94

I

(100), 91, >99:1 d.r.

(68)

(72), 92, >95:5 d.r.

Product(s) and Yield(s) (%), % ee

I (96), 46, >99:1 d.r.

F

F

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

50

132

37

37

519, 37

348

491

Refs.

271

O

AcO

OR

TBDMSO

TBDPSO

i-Pr

i-Pr

t-Bu

O

O

O

H

H

H

H

O H

O H

O H

O

O O

B

O

B

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B[(–)-Ipc]2

B[(–)-Ipc]2

B

O

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

THF, –78°, 6 h

4 Å MS, toluene, –78°

THF, –78°, 4 h

THF, –78°, 4 h

Neat, rt, 4 d

AcO

OR

OH

OH

OH

OH

TBDMSO

TBDPSO

i-Pr

i-Pr

t-Bu

OH

(54)

H

(—)

1:1

2:1

(—) Ac

d.r. 50:1

(71) Bz

R

OH

(75), 94:6 d.r.

OH

(70)

(56)

(72), 98:2 d.r.

(65), >97:3 d.r.

640

639

638

637

554

554

521

272

C7

TBDPSO

TBDPSO

TBDMSO

TBDMSO

O

O

H

H

Carbonyl Substrate

O

O

O

O B O

O

O

OPr-i

OPr-i

B[(+)-Ipc]2

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

O

B[(+)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

18 h

4 Å MS, toluene, –78°,

12 h

BF3•OEt2, THF, –78°,

12 h

BF3•OEt2, THF, –78°,

18 h

4 Å MS, toluene, –78°,

18 h

4 Å MS, toluene, –78°,

12 h

BF3•OEt2, THF, –78°,

12 h

BF3•OEt2, THF, –78°,

Conditions

OH

I (45), 85:15 d.r.

TBDMSO

I (78), 98:2 d.r.

I (72), 98:2 d.r.

TBDPSO

OH

(85), 90:10 d.r.

TBDMSO

I (70), 98:2 d.r.

I (75), 98:2 d.r.

TBDPSO

OH

I (70), 70:30 d.r.

TBDMSO

Product(s) and Yield(s) (%), % ee

TBDPSO

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

641

641

641

641

641

641

641

Refs.

273

HO O

H

O

OBn

TBDMSO

TESO

O

OH

OTBDMS

TBDMSO

TBDPSO

TBDMSO

TBDPSO

OMe

OTBDMS

O

O

O

O

H

H

H

O H

O

O

O

O

O

O

O

O

O

O B O

CF3

N

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

N

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

B

O

B

O

B

O

O

CF3

100°, 3.5 d

4 Å MS, 40°, 25 h;

BF3•OEt2, THF, –78°

toluene, –78°, 1.5 h

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Toluene, –75°

18 h

4 Å MS, toluene, –78°,

OH

O

OH

O

OH TBDMS

(67), >10:1 d.r.

O

OBn

(72), >98:2 d.r.

OH

(90)

(53)

OH

(78)

(—), >9:1 d.r.

TESO

OH

TBDMSO

OH

TBDMSO

TBDPSO

TBDMSO

TBDPSO

OMe

OTBDMS

I (52), 98:2 d.r.

643

464

649

364

553

642

641

274

C8

Ph

O

n-C7H15

n-C5H11

O

O H

O

O

H

H

Carbonyl Substrate

DMF, –40°, 3 h

(R,R)-i-Pr-DuPHOS,

DMF, –40°, 1 h

CuF, La(OPr-i)3,

(R,R)-i-Pr-DuPHOS,

4h

4 Å MS, toluene, –78°,

B

O

OPr-i

OPr-i

CuF, La(OPr-i)3, O

O

O

O

CH2Cl2:H2O, rt, 15 min

n-Bu4NI (10 mol%),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

CH2Cl2, –78°, 15 min

BF3•OEt2 (2 equiv),

THF, –78° to rt

CH2Cl2, –78°, 24 h

Sc(OTf)3 (10 mol%),

Conditions

O

B

O

B

O

"

"

BF3–K+

B[(+)-Ipc]2

Ph

O B O

Allylborane Reagent

I

OH

OH

OH

Ph

HO

HO

(72), 95:5 d.r.

(80), 93, 73:27 d.r.

(73), 90, 70:30 d.r.

OH

I (96), >98:2 d.r.

(84), >98:2 d.r.

(86), >95, >97.5:2.5 d.r.

(60), 97, >49:1 d.r.

Product(s) and Yield(s) (%), % ee

I (85), >98:2 d.r.

n-C7H15

n-C7H15

n-C5H11

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

164

164

644, 645

100

99

98, 99

322

28

Refs.

275

TIPSO

BnO

TBDMSO

4

4

PMBO

BnO

PMBO

TBDMSO

Ph

O

O

H

H

H

OTBDMS

O

O

O

H

H

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

"

BF3–K+

THF, –78°

Ether, –78°, 3 h

Ether, –78°, 3 h

THF, –78°

THF, –78°

THF, –78°

THF, –78°

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

30 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

OH

4

4

4

TBDMSO

TIPSO

TIPSO

I (—)

BnO

PMBO

BnO

PMBO

BnO

PMBO

OH

OH

(85), >97.5:2.5 d.r.

OH

(—)

(—), 1:1 d.r.

(—)

(99), 90:10 d.r.

OTBDMS

(56), 9:1 d.r.

(51), 9:1 d.r.

I

OH

OH

OH

I (82), 90:10 d.r.

TBDMSO I

Ph

590

646

646

543

543

543

543

99

276

276

C8

O

n-Pr

PMBO

HO2C

BnO

TBDPSO

OBn O

Ph

OTES O

O H

OBn O

H

H

TBDMSO

OBn OBn

TBDMSO

Carbonyl Substrate

H

O

O

O

O

O

O B O

O

B(OPr-i)2

B

O

B

O

B

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Allylborane Reagent

4 Å MS, toluene, –78°

–10° to rt

Et3N, CH2Cl2,

–78° to rt, 15 h

4 Å MS, toluene,

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Conditions

n-Pr

PMBO

HO2C

OBn OH (—), 9:1 d.r.

(96), 99:1 d.r.

OTES OH (93), >99:1 d.r.

OBn OH

(—), 2.5:1

OBn OBn

HO Ph

BnO

TBDPSO

OH

(78), >99:1 d.r.

TBDMSO

Product(s) and Yield(s) (%), % ee

TBDMSO

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

559

106

648

647

619

Refs.

277

C9

Ph

Et

O

n-C5H11

Ph

O

N

H

O

O H

OPMB O

O

H

H

O H

O

N Ts

Ph

O

O O

O

O

Ph

O B O

B

O

B

O

B

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

BF3–K+

B

Ts N

Ph

B[(–)-Ipc]2

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

O

CH2Cl2, –78°, 24 h

Sc(OTf)3 (10 mol%),

3h

4 Å MS, toluene, –78°,

—

—

THF, ether, –78°, 15 h

n-Bu4NI (10 mol%), CH2Cl2, H2O, rt, 15 min

THF, –78°

Ether, –78°, 5 h

THF, –70°, 6 h

4 Å MS, toluene, –78°

O

N

Ph

Ph

Et

HO

Et

HO

H

OH

OH

OH

OH

OH

OPMB

OH

OBn OBn OH

OBn OH

OPMB H O

O

n-C5H11

Ph

Ph

Ph

n-Pr

PMBO

(71), 96, >49:1 d.r.

(89), 86, 99:1 d.r.

(90), 68:32 d.r.

(83), 80:20 d.r.

(34), 4:1 d.r.

(99), >98:2 d.r.

(74-82), 91-95

(69), 89, >99:1 d.r.

(67), >92, >96:4 d.r.

(—), 1.2:1 d.r.

27, 28

519, 37

197

197

650, 651

100

50

292

374

559

278

C10

C9 O

n-C6H13

n-C7H15

Ph

TBDMSO

i-Pr

i-Pr

Ph H

O

O

H

H

H

O

O

O

H

H

Carbonyl Substrate

O

O

O

O

O

B

O

B

O

"

O

O

O

O

BF3–K+

B

O

B

O

B

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Allylborane Reagent

4 Å MS, toluene, –78°

toluene, –78°

Cr(CO)3, 4 Å MS,

30 min

CH2Cl2/H2O, rt,

n-Bu4NI (0.1 eq),

CH2Cl2, rt, 3-6 h

BF3•OEt2 (5 mol%),

2h

4 Å MS, toluene, –78°,

2h

4 Å MS, toluene, –78°,

Neat, rt, 4 d

Conditions OH

n-C6H13

n-C7H15

Ph

TBDMSO

Ph

OH

OH

OH

OH

OH

OH

(55-70), 69

(85-95), 96, 97:3

(96), 75:25 d.r.

(87), 75:25 d.r.

(70), 95.5:4.5 d.r.

(70), 97:3 d.r.

(53), 75:25 d.r.

Product(s) and Yield(s) (%), % ee

TBDMSO

i-Pr

i-Pr

Ph

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

130

128

276

99

526

526

521

Refs.

279

PMBO

PMBO

t-Bu

PMBO

n-C9H19

n-C7H15

O H

O

O

H

OR

H

DEIPSO

O

H

H OAc

O

OAc

O

O

O

O

O

O

B

O

B

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

B

O

B

O

O

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

12 h

THF, –100° to –78°,

3h

4 Å MS, toluene, –78°,

4h

4 Å MS, toluene, –78°,

toluene, –78°

Cr(CO)3, 4 Å MS,

OH

PMBO

PMBO

(67)

OR

DEIPSO

TBDMS

R

O

OAc

OH

OAc

OH

(97)

(91), 74, >99:1 d.r.

(55-70), 28

(90), 88, >99:1 d.r.

OH

OH

OH

(53), >97.5:2.5 d.r.

t-Bu

PMBO

n-C9H19

n-C7H15

n-C6H13

653, 196

652

313

519, 37

519, 37

130

280

C11

C10

n-Pr

BnO

MeO

H

TBDPSO

TBDPSO

TBDPSO

O H

OBn

OMe

O

H

O

O

O

O

O

TESO

OBn O

O

O

O

H

O

O

Carbonyl Substrate

N

O

N

O

O

O

H Pr-i

O

H

H

B

O

B

O

B

O

B

O

B

O

O

O

O

O

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Allylborane Reagent

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

Conditions

BnO

MeO

n-Pr

O

O H I H

OBn

OMe

O

OH

O

O

O

O

TESO

OBn OH

(—), 85:15 d.r.

TBDPSO

(—), 3:2 d.r.

TBDPSO

O

(90), >99:1 d.r.

O

O

O

(71)

O

OH Pr-i

O

(80), 2.2:1 d.r.

N

N

OH

OH

Product(s) and Yield(s) (%), % ee

TBDPSO

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

559

655

654

654

654

Refs.

281

C12

MeO

MeO

Cy

Ph

n-Pr

BnO

O

N

H

O

O

O

H

H

H

OBn O

PMBO

H

OBn

O

O

H

H

O

O

O

O

O

B[(+)-Ipc]2

THF/ether, –78°, 15 h

THF/ether, –78°, 15 h

—

"

B[(+)-Ipc]2

THF/ether, –78°, 15 h

THF

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

B[(+)-Ipc]2

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

B

O

B

O

O

H I

O H

OBn OBn OH

MeO

MeO

Cy

I (80)

Ph

O

N

OH

OH

(65), 7:1 d.r.

(79), 7:1 d.r.

(80), >99:1 d.r.

(52), 5:1 d.r.

OH

I

OH

(53), 6:1 d.r.

PMBO

I (80), >99:1 d.r.

n-Pr

BnO

I (80), >99:1 d.r.

650, 651

650, 651

656

650, 651

374

559

559

559

282

C13

C12

O

OTBDMS

TMSEO2C

TBDPSO O

O

O

TESO

H

OAc

O

O

O

BnO

O

OBn O

H

H

H

O H

OBn O

OAc O

O

O

Carbonyl Substrate

H

H

O

O

O B O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

O

O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

O

Allylborane Reagent

—

THF, –78° to rt, 1 h

4 Å MS, toluene, –78°

—

Toluene, –78°

Conditions

OTBDMS

TMSEO2C

O H

O

O H

OAc

OH

(77), 14.1:1 d.r.

O

OBn OH

(77)

(71)

(82)

OAc OH

OH

OH

TESO (82), >98.5:1.5 d.r.

O

O

O

Product(s) and Yield(s) (%), % ee

TBDPSO

BnO

O

OBn O

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

657, 658

445

654

561

334

Refs.

283

C14

Et

Et

OH

O Ph

TsO

TBDMSO

Ph

Ph

TBDMSO O

O

O

H

O

O

O

N O

OAc O

O

H

H

H O O

O O

OPr-i

OPr-i

B[(–)-Ipc]2

B

O

O

B(OPr-i)2

B[(–)-Ipc]2

"

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

Ether, THF, –78°

—

0-40°, 24 h

Et3N, CH2Cl2,

Et

Et

OH

OH

O

N

O

TsO (61)

(—), 5:1 d.r. OH

OH

(60), 7:1 d.r.

(69), 7:1 d.r.

O (90), 88, >99:1 d.r.

O

OAc OH

OH (83), 99:1 d.r., >99:1 syn:anti

HO Ph

TBDMSO

Ph

Ph

—

I I (80), >99:1 d.r.

Ph

O

THF, ether, –78°, 15 h

THF, –78°, 15 h

3h

4 Å MS, toluene, –78°,

TBDMSO

629, 630

629

109

660

659

656

260

284

C15

C14

PMBO

O H

O

OPr-i

OPr-i

THF, –78°, 18 h

—

—

—

30 min

CH2Cl2, H2O, rt,

n-Bu4NI (10 mol%),

O

t-Bu

O

Si O

Bu-t

Pr-i

B

O O

O

O

OPr-i

OPr-i —

I

Ph

OBn O

t-Bu

O

Si

O

Bu-t PMBO

OH

(70), 4:1 d.r.

(65), 1.5:1 d.r.

Pr-i

(68), 75:25 d.r.

(—), 4:1 d.r.

C6H13-n

OH

Pr-i

OH

I (—), 3:1 d.r.

I (—), 2:1 d.r.

Ph

N

MeO2C OH

n-C11H23

TBDMSO

N

O

O

O

B[(+)-Ipc]2

B

O

B

O

B[(+)-Ipc]2

BF3–K+

Product(s) and Yield(s) (%), % ee

MeO2C H

H

n-C6H13

Conditions

N

O

Pr-i

H

O

Allylborane Reagent

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

MeO2C O

N

OBn O

Ph

Ph

MeO2C O

n-C11H23

TBDMSO

Carbonyl Substrate

334

661, 662

661

661

661

276

Refs.

285

C18

C17

C16

O

i-Pr

BnO

R 1O

H

O

O

O

O

O H

H

O

OMe O

OMEM

BnO

OTBDPS

OTBDMS

O

OTBDMS

O

H

O

O

H

OR2

OMe

O

NH2 n-C13H27

MEMO

R

H

H

O O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

O

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

THF, –78°, 3 h

–78°

THF, –78°, 4 h

1h

BF3•Et2O, THF, –78°,

15 h

THF, ether, –78°,

i-Pr

BnO

R1O

R

OH

O

H (73)

OTBDMS

OTBDMS

O

NH2 n-C13H27

O

OH

(82)

(55)

Bz O

(66)

TBDMS TBDMS

OMEM

OMe OH

(60)

TBDMS

O

BnO

OTBDPS

(72)

(70)

R2

OR2

OMe

H

O

O

2-Nph

1-Adm

R

R1

O

OH

MEMO

OH 8:1

5:1

d.r.

607

663

168

533

650, 651

286

C19

H

O

MeO

O O H

OPiv

H

O OPiv

O

H

O

O

OTES O

OBn OMe

MEMO

H

BnO

MeO MOMO

MeO

O H

H

O

OTBDPS

BnO

H

Carbonyl Substrate

O

B

O O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

B

O

O

B[(–)-Ipc]2

Allylborane Reagent

4 Å MS, toluene, –78°

1h

BF3•Et2O, THF, –78°,

1.5 h

4 Å MS, toluene, –78°,

–78°

Conditions

MeO

H

H

H (92), 4:1 d.r.

O

OPiv

OPiv

O

OBn OMe

MEMO

O

OH

O

BnO

MeO MOMO

OTES OH

OTBDPS

OH

(40), 1.3:1 d.r.

BnO

OH

(92), 4:1 d.r.

H

O

O

(83)

Product(s) and Yield(s) (%), % ee MeO

TABLE 3. ADDITION OF E-CROTYL REAGENTS (Continued)

665

533

664

361

Refs.

287

C24

C22

H

O

TBDMSO

OR1

O

OR2 O

H

H

OH MeO

H

O

H

OMEM

H

OMe

H

OMe OR3

O

O

H

O

H

H

B

O

B

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B[(+)-Ipc]2

4 Å MS, toluene, –78°

4 Å MS, toluene, –78°

THF, –78°, 4 h

OH MeO

H

H H

(—)

OH

OMe

H

d.r.

30:40

39:35

31:22

48:0

OH

OH

(92)

TBDPS

TBDMS

TBDMS

TBDMS

(97), 9:1 d.r.

H

Bz

Bz

O

Bz

Bz

O

TBDMS

Bz

H

TBDMS

TBDMS

R3

OMe OR3

OMEM

H

R2

O

R1

O

TBDMSO

OR1

OR2

666, 667

579

630, 578,

168

288

C2

C1

O

O

O

H

O

Carbonyl Substrate

Ph

Ph

Ph

O

B

Br

Cl

Cl

Cl

O

O

O

O

O

O

Ph

O

Cy

OBn

Cy

R

Ph

OH

B

O

B

O

B

O

B

B

OH

Allylborane Reagent

–78°, 2 h; rt, 24 h

Neat, 0°, 15 h

THF, –78° to rt, 18 h

Neat, 0°, 15 h

Neat, 0°, 15 h

Toluene, 80°

Conditions

Ph

OH

OH

OH

OH

Br

Cl

Cl

Cl

4:1

(78)

i-Pr n-Pr

OBn

(95), >95

(78), 7:93 E:Z

(78), >99, >78:1 Z:E

(—), 92, 5:95 E:Z

6:1

d.r. (79)

R

(63), 7:93 E:Z

R

OH

Product(s) and Yield(s) (%), % ee

HO

OH

OH

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS

670

146, 668

65

66, 669

146, 668

236

Refs.

289 Me

Me

O

B

O

O

Cl

O

O

O

B

O

B

O O

O

SO2Me

B

O

Ts

OPh

N

N

B

O

OMe "

B

CH2Cl2, 0° to rt, 15 h

24 h

Petroleum ether, rt,

2. H+, MeOH

1. 4 kbar, rt, 3 d

4 kbar, rt, 3 d

–78° to rt, 2 d

Petroleum ether,

20°, 60 h

Ether, –70° to rt, 16 h

OH

OH

MeO

OH

I (64), 94

I

OH

OH

O

Cl

OPh

(48), 96:4 d.r.

(69), 97:3 d.r.

(53-64), 95:5 d.r., 5:95 E:Z

(54), 5:95 E:Z

N Ts

(64), 94, >95:5 Z:E

Me

OMe

(71), 21:79 E:Z

67

68

672

672

68

147

148

290

C2

O

H

Carbonyl Substrate

n-Bu

n-Bu

n-Bu

Cl

Cl

B

O

B

O

Cl

O

O

"

B

O

B

O

B

O

B

O

O

O

O

O

Allylborane Reagent

Neat, rt, 5-8 d

Neat, rt, 5-8 d

Neat, rt, 5-8 d

CH2Cl2, 0° to rt, 15 h

CH2Cl2, 0° to rt, 15 h

12 h

Petroleum ether, rt,

18 h

Petroleum ether, rt,

Conditions

Cl

Cl

Cl

I

Bu-n

OH

Bu-n

I (73), 97:3 d.r

OH

(70), 87, 97:3 d.r.

(79), 96:4 d.r.

(70), 97:3 d.r., 85:12 E:Z

(53-60), 92, 95:5 d.r.

(53-64), 95, 95:5 d.r.

I (70), 73, 97:3 d.r.

I

OH

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

673

673

673

67

67

83

67

Refs.

291

RO H

R = TBDMS

R = Bn

O

O

B

Ph

n-C5H11

Bu-n

Bu-n

Bu-n

O

OH

B

O O

HO

B

O

B

O

B

O

B

O

O

O

Cy

Cy

OPMB

O B O

—

45 min; rt, 24 h

PhMgCl, –15°,

Cl

THF, –15° to rt

Neat, rt, 5-8 d

Neat, rt, 5-8 d

Neat, rt, 5-8 d

,

RO

RO

Bu-n

Bu-n

Bu-n

OH

OH

C5H11-n

OH

OH

OH

OH

OH

(35), 2:98 E:Z

OPMB

(76), 50, 96:4 d.r.

(73), 94

Ph

Cy

(53), 91, 97:3 d.r.

(70), 93, 96:4 d.r.

(69), 96:4 d.r

202

87

674

673

673

673

292

C3

O H

Carbonyl Substrate

O

B

O

B

O

B

O

B

O

O

O

O

O

Cl

B

O

B

O

SiMe2Ph

Br

Cl

Cl

Cl

B

O

O

O

Cy Cy

Allylborane Reagent

CH2Cl2, 0° to rt, 15 h

–78° to rt

Petroleum ether,

THF, 100°, 24 h

Neat, 0°, 15 h

THF, –78° to rt, 18 h

Neat, 0°, 15 h

Neat, 0°, 15 h

Conditions

Cl

I

OH

OH

OH

OH

OH

(74), 15:85 E:Z

(82), 6:94 E:Z

Cl

(47-65), 95:5 d.r., 5:95 E:Z

(81), 35:65 E:Z

SiMe2Ph

Br

Cl

(86), 6:94 E:Z

(81), >99, >81:1 Z:E

I (—), 89, 4:96 E:Z

I

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

67

676

675

146, 668

65

66, 669

146, 668

Refs.

293 Me

Me

B

O

B

O

N

N

O

O

O

O

O

O

SO2Me

B

O

Ts

B

O

OPh

B

O

OMe "

Cl

O B

CH2Cl2, rt, 20 h

2. H+, MeOH

1. 4 kbar, rt, 3 d

4 kbar, rt, 3 d

24 h

Petroleum ether, rt,

20°, 60 h

–78° to rt, 2 d

Petroleum ether,

12 h

Petroleum ether, rt,

OMe

MeO

OH

OH

OH

O

(62), 97:3 d.r.

(92), 96:4 d.r.

(81), 97:3 d.r.

N

Ts

(57), 5:95 E:Z

(81), 90, 97.5:1.5 d.r.

Me

OPh

I (81), 90, >95:5 Z:E

OH

I (47-65), 96, 95:5 d.r.

676

672

672

68

147

68

83, 67

294

C3

O H

Carbonyl Substrate

O

B

O

B

TBDMSO

BnO

RO

Cl

Cl

B

O

B

O

Cl

Cy

Cl

O

O

O

Cl

O

B

O

B

O

O

Cy

O

Allylborane Reagent

Neat, rt, 10 h

Neat, rt, 10 h

Neat, rt, 10 h

Petroleum ether

CH2Cl2, 0° to rt, 15 h

CH2Cl2, 0° to rt, 15 h

Conditions

OR

Cl

TBDMSO

OH

Cl

OBn Cl

OH

OH

OH

I (81), 85, 97:3 d.r.

I

OH

TBDMS

Bn

R

(62)

(62)

(55)

(81), 97:3 d.r., 91:6 E:Z

(85), 99

(55)

Cl

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

67

67

67

628, 197

67

67

Refs.

295

O

"

Bu-n

n-Bu

O

B

B

O

O

Pr-i

O

O

O

BBN

B

O

B

O

C5H11-n

B

O

O

, rt, 24 h

HBBN, pentane,

8 kbar, 3 d

Petroleum ether,

8 kbar, 3 d

Petroleum ether,

2. Ketone, rt, 2 h

1.

Pentane, rt, 2 h

Neat, rt, 5-8 d

Neat, rt, 5-8 d

CH2Cl2, rt, 18 h

Bu-n

Bu-n

Pr-i

(—), 98:2 E:Z

(85)

(80), 97:3 d.r.

(85), 97:3 d.r.

(51), 1:9 E:Z C5H11-n

I (—), 33:67 E:Z

I

OH

I (80)

I

OH

OH

OH

OH

102

102

103

103

673

673

677

296

C3

O

O

O

OBn

BnO

O

H

n-C5H11S

H

O H

O H

Carbonyl Substrate

O

Cl

Cl

Cl

Cl

B

O

B

O

B

O

B

O

B

O

O

OH

O

O

O

O

Cy

Cy

Cy

Cy

O

C5H11-n

B

O

Cy

Cy

Cy

Cy

OBu-t

Allylborane Reagent

–30° to rt, 18 h

(MeO)2CH2,

–30° to rt, 18 h

(MeO)2CH2,

–30° to rt, 18 h

(MeO)2CH2,

–30° to rt, 18 h

(MeO)2CH2,

–78° to rt

CH2Cl2, rt, 18 h

Conditions

OH

O

O

O

O

OBn

OH

OH

OH

I

Cl

Cl

OH O

Cl

Cl

(72), 96:4 d.r.

(67), 92:8 d.r.

(74), 97:3 d.r.

OBu-t

(64), 1:9 E:Z C5H11-n

(73), 92:8 d.r.

(36-77), 83->95

OH

OBn

BnO

n-C5H11S

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

65

65

65

65

203

677

Refs.

297

Cl

Cl

O

R

Ph Ph

O

B

Ph OMe OMe

Ph O

R

Ph Ph

O

B

Ph OMe OMe

Ph

O

O

O

B

O

B

Toluene, –100° to rt

Toluene, –100° to rt

CH2Cl2, 15 h

CH2Cl2, 15 h

O

O

O Cl

d.r.

(75)

C(O)NMe2

68:32

d.r. 69:31 (89)

>99:1

>99:1

CO2Et

R

R

R

O

(63)

C(O)NMe2

OH

(86)

CO2Et

R

O

OH

(39), 72, 90:10 d.r., 12:88 E:Z

O

OH

I (45), 96, 96:4 d.r., 6:94 E:Z

85

85

66

66

298

C3

O

O

O H

Carbonyl Substrate

Ph

B

O

Ph

O

B

O

Ph

O

O

Ph

Ph

O

OR

B

OR

OH OTBDPS

Allylborane Reagent

O

O

2

B ,

P NMe2,

Pd2(dba)3, 22°, 10 h

O

O

Ph,

O

Ar Ar

Ar Ar O

Ar = 3,5-Me2C6H3

3. NaOH, H2O2

2. Aldehyde, 22°, 14 h

1.

CH2Cl2, rt

Conditions

O

O

O

OH

O Ph

9:1

4:1

t-Bu (70-90)

d.r. (57)

PMB

OR

OH

R

O

OH

OTBDPS

(73), 21:1 d.r.

OR

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

187

201

Refs.

299

MeO

O

O

O

O

BBN

O

B

O

B

SnMe3

B

O

B

O

O Ph

O

O

O

2

B ,

P NMe2,

Pd2(dba)3, 22°, 10 h

O

O

Ph,

O

Ar Ar

Ar Ar O

30 min

Ether, –76° to 0°,

24-48 h

CH2Cl2, –78° to rt,

24-48 h

CH2Cl2, –78° to rt,

Ar = 3,5-Me2C6H3

3. NaOH, H2O2

2. Aldehyde, 22°, 14 h

1.

MeO

O

O

O

OH

O Ph (60), >21:1 d.r.

O

OH

SnMe3

(60)

(75-85), 92, 94:6 d.r., 94:6 anti:syn

O

OH

(75-85), 56:44 d.r., >99:1 anti:syn

O

O

OH

598

537, 118

537, 118

187

300

C4

C3

MeO

O

O

O

H

O

H

Carbonyl Substrate

R

Cl

B

O

B

O

TMS

O

O

BBN

Allylborane Reagent

CH2Cl2, rt, 18 h

5d

Petroleum ether, rt,

30 min

Ether, –76° to 0°,

Conditions

MeO I

E:Z 1:9 9:91 11:89 12:88 12:88 1:9

(80) (75) (79) (62) (83)

Cl

t-Bu Ph

I:II = 63:37

I + II (65),

(82)

(65), >90

TMS

+

n-C5H11

R

II

Cl

O

OH

TMS

R

OH

OH

MeO

O

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

677

678, 679

598

Refs.

301

n-Pr

O H i-Pr

O

O

N

N B

B

O

O

Pr-i

O

Ts

B R

O

Ts

N

O

2

B ,

P NMe2,

Pd2(dba)3, 22°, 10 h

O

O

R,

O

O Ar Ar

Ar Ar O

Ar = 3,5-Me2C6H3

3. NaOH, H2O2

2. Aldehyde, 22°, 14 h

1.

Toluene, 60°, 72 h

n-Pr

n-Pr

OH

OH

(85), 94 (89), 86 (88), 91 n-C10H21

Pr-i

(58), 85, >95:5 Z:E

Cy

R

N

O

Ph

R

O

i-Pr

O

187

51

302

C4

i-Pr

O H

Carbonyl Substrate

Cl

Cl

Cl

Br

B

O

B

O

B

O

O

O

O

BCy2

R R

Allylborane Reagent

Cy2BH

Br,

Neat, 0°, 15 h

Neat, 0°, 15 h

Neat, 0°, 15 h

n-Bu4NBr, 0°

2. Aldehyde,

1.

Conditions

i-Pr

i-Pr

i-Pr

i-Pr

61:39 (78) (74)

CH2OMe OCH2C6H4Cl-p

82:18

E:Z 34:66 (68)

Cl

(—), 92, 5:95 E:Z

(83), 4:96 E:Z

Ph

Cl

Cl

Br

(46), 16:84 E:Z

R

OH

OH

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

146

66

669

146, 668,

680

Refs.

303 SR

Br

Cl

B

O

B

O

B

O

B

O

O

O

O

O

Cy Cy

Neat, 0°, 15 h

Neat, 0°, 15 h

Neat, 0°, 15 h

THF, –78° to rt, 18 h

i-Pr

i-Pr

i-Pr

i-Pr

OH

OH

OH

OH

SR

Br

Cl

(63)

(84)

E:Z 20:80

15:85

(72), 21:79 E:Z

Bu-t

Et

R

(83), 4:96 E:Z

(89), >99, >89:1 Z:E

146

146, 668

146, 668

65

304

C4

i-Pr

O H

Carbonyl Substrate

O O

B

O

B

O

OMe

B

O

B

O

O

O

O

O

Allylborane Reagent

2. I2, 110°

1. Toluene, rt, 2 d

Neat, 0°, 15 h

Neat, 0°, 15 h

16 h

Ether, –70° to rt,

Conditions

i-Pr

i-Pr

i-Pr

i-Pr

OH

OH

OH

OH

OMe

O H

(90-94)

(94), 60:40 E:Z

(55), >95:5 Z:E

(72), 21:79 E:Z

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

207, 208

146

146, 668

148

Refs.

305 Me

B

O

B

O

"

N Ts

B

O

"

OMe

Cl

Cl

B

O

O

O

O

O

4 kbar, rt, 3 d

20°, 60 h

–78° to rt, 2 d

Petroleum ether,

CH2Cl2, 0° to rt, 15 h

18 h

Petroleum ether, rt,

12 h

Petroleum ether, rt, I

Cl

(54-84), 95

I

OMe

i-Pr

OH

N

Me

I (82), 90, >95:5 Z:E

i-Pr

OH

Ts

(75), 98:2 d.r.

(82), 90

I (55-84), 95:5 d.r., 5:95 E:Z

I (55-84), 96, 5:95 E:Z

i-Pr

OH

672

147

68

67

67

83

306

C4

i-Pr

O H

Carbonyl Substrate

BnO

O

O

Ts

N

O

B

O

B

Pr-i

Cl

Cl

B

O

O

B

N

B

O

Cy

Cl

O

O

O

O

Cy

Ts

N

SO2Me

N(Pr-i)2

Me

B

O

Allylborane Reagent

Neat, rt, 10 h

3d

Petroleum ether, rt,

15 h

CH2Cl2, 0° to rt,

15 h

CH2Cl2, 0° to rt,

Toluene, 60°, 72 h

2. H+, MeOH

1. 4 kbar, rt, 3 d

Conditions

I

OH

OH

O

O

O

Cl

i-Pr

i-Pr

OBn Cl

OH

OH

(62)

Pr-i

(77), 99, 80:20 d.r.

96:4 E:Z

(58), 91, 96:4 d.r.,

(71), 84, 6:94 E:Z

(76), 96:4 d.r.

N(Pr-i)2

Pr-i

I (58), 97:3 d.r., 91:6 E:Z

i-Pr

i-Pr

MeO

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

67

681

67

67

51

672

Refs.

307

R

"

B

O O

B

O O

Ar = 3,5-Me2C6H3

Bu-n

n-Bu

B

O

Ar = 3,5-Me2C6H3

O

B

O

O

O

O

2

B ,

O

O

2

B ,

22°, 14 h

Neat, rt, 5-8 d

Neat, rt, 5-8 d

i-Pr

i-Pr

I

P NMe2,

Pd2(dba)3, aldehyde,

O

O

R,

O

Ar Ar

Ar Ar O

2. NaOH, H2O2

1.

3. NaOH, H2O2

i-Pr

P NMe2,

Pd2(dba)3, 22°, 10 h

O

O

R,

O

Ar Ar

Ar Ar O

2. Aldehyde, 22°, 14 h

1.

O

OH

OH

Bu-n

Bu-n

n-C10H21

Ph

R

I

OH

Cy

n-C10H21

Ph

R

(83), 87

(96), 91

(89), 95

(76), >99:1 d.r.

(85), 98:2 d.r.

(68), 88

(80), 92

R

673

673

187

187

308

C5

C4

N

H

O

O

OMe

Cy

O

MeO

Et

i-Pr

O

O

H

H

O H

Carbonyl Substrate

O

O

Ts

B

O

O

B

N B

O

Ts

N

BBN

B

O

O

TMS

B

O

HO

N(Pr-i)2

n-C5H11 Ipc-(–)

Ipc-(–)

Allylborane Reagent

CH2Cl2, rt, 20 h

Toluene, 60°, 48 h

30 min

Pyr, ether, –78°,

8 kbar, 3 d

Petroleum ether,

8 kbar, 3 d

Petroleum ether,

THF, –15° to 15°

Conditions

MeO

Et

Et

i-Pr

O

O

OH

OMe

OH

OH

OH

O

(60), 85, >95:5 Z:E

(90), 90:10 d.r.

N(Pr-i)2

O

TMS

(40)

(—), 72:28 d.r., 29:71 E:Z

(—), 1:1 d.r., 98:2 E:Z

Ipc-(–) (62), 85, 96:4 d.r.

OH

C5H11-n

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

676

51

682

102

102

674

Refs.

309

i-Pr

n-Bu

Et

O

O

H

O

H

H

O H

Me

BnO

Cl

Br

O

Cl

Cy

Ts

B

O

O

O

O

B

O O

B(OMe)2

N

B

O

B

O

B

O

B

O

Cy

O

Ether, –70° to rt, 16 h

Ether, –70° to rt, 16 h

2. H+, MeOH

1. 4 kbar, rt, 3 d

Neat, rt, 10 h

THF, –78° to rt, 18 h

Neat, rt, 15 h

–78° to rt

Petroleum ether,

I

OH

O

OH

OH

Cl

Cl

(85), 8:92 E:Z

(90), 23:77 E:Z

(—), 76:24 E:Z

(87), 98:2 d.r.

(61)

(76), 99, 1:76 E:Z

Br

Bu-n

OBn

I (—), 51:49 E:Z

i-Pr

MeO

n-Bu

Et

OH

OH

148

148

672

67

65

146, 668

676

310

C5

Et

i-Pr

i-Pr

O

O

O

H

H

Carbonyl Substrate

O

B

N

O

O

Cl

B

O

B

O

B

O

O

N(Pr-i)2

O

Ts

B

B

O

O

O

Ts

N

O

Allylborane Reagent

0° to rt, 12 h

Petroleum ether,

8 kbar, 3 d

Petroleum ether,

8 kbar, 3 d

Petroleum ether,

Toluene, 60°, 72 h

Ether, –70° to rt, 16 h

Ether, –70° to rt, 16 h

Conditions

I

OH

i-Pr

i-Pr

Et

OH

O

I

OH

OH

OH (—), 49:51 d.r., 98:2 E:Z

N(Pr-i)2

O

(75), 31:69 E:Z

Cl

(—), 80:20 d.r.

(—), >99:1 d.r., 25:75 E:Z

(69), 85, >95:5 Z:E

i-Pr

I (—), 41:59 E:Z

i-Pr

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

149

102

102

51

148

148

Refs.

311

Et

O H

B

O

B

O

B

O

B

O

"

OMe

B

O

OMe

Cl

Cl

O B

O

O

O

O

O

O

0° to rt, 18 h

Petroleum ether,

18 h

Toluene, 0° to rt,

20°, 60 h

60 h

Toluene, –78° to rt,

60 h

Toluene, –78° to rt,

12 h

Petroleum ether, rt,

12 h

Petroleum ether, rt,

I

OH

OH

OH

Et

Et

OH

OH

I (48), >95:5 d.r.

Et

Et

Et

(50-60), 98:2 d.r.

(59), 90, >99:1 d.r.

Cl

(44), 90:10 d.r.

(56), >98:2 d.r.

OMe

(59), 99, >99:1 d.r.

OMe

I (50-60), 90:10 d.r.

149

149

147

68

68

83

83

312

C6

n-C5H11

Et

O

O

H

H

H

O

Carbonyl Substrate

TMS

TMS

TMS

BBN BBN BCy2 BCy2 BBN BBN BCy2 BCy2

Me Me Me Me n-Bu n-Bu n-Bu n-Bu

R2

Cy

R2

O

Cy

R1

R1

B

O

BCy2

BBN

Allylborane Reagent

—

3d

Petroleum ether, rt,

—

—

Conditions

TMS

I

III

R1

+

(77) (80) (78) (70) (68) (65) (77) (73)

H2SO4 NaOH H2SO4 NaOH H2SO4 NaOH H2SO4

II

R1

IV

R1

+

0:0:9:91

0:0:97:3

1:93:2:4

97:1:2:0

0:0:8:92

0:0:98:2

1:90:3:6

94:1:4:1

I:II:III:IV

n-C5H11

n-C5H11

(81), 99

>95:5 Z:E

(93), >98:2 d.r.,

I + II + III + IV

R1

+

NaOH

Work-Up

n-C5H11

n-C5H11

Et

OH

I (92), >99:1 d.r., >95:5 Z:E

I

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

684

681

683

683

Refs.

313 n-C5H11

BnO

Br

B

O

B

O

B

O

O

HO

Cl

OPh

B

O

OMe

Cl

Cl

B

O

B

B

O

O

O

O

O

Ipc-(–)

Ipc-(–)

O

THF, –15° to 15°

Neat, rt, 10 h

24 h

Petroleum ether, rt,

–78° to rt, 2 d

Petroleum ether,

CH2Cl2, 0° to rt, 15 h

12-18 h

Petroleum ether, rt,

Neat, 0°, 15 h

I

OH

Cl

Br

(60-91), 92, 95:5 d.r.

(69), 8:92 E:Z

n-C5H11

n-C5H11

n-C5H11

n-C5H11

C5H11-n

OH

(61)

96:4 d.r.

(62), 85,

(49), 5:95 E:Z

(87), 88

Ipc-(–)

OPh

OMe

OBn Cl

OH

OH

OH

I (60-91), 95:5 d.r., 5:95 E:Z

n-C5H11

n-C5H11

OH

674

67

68

68

67

67

83, 67,

146, 668

314

C6

O

Et

TBDMSO

t-Bu

O

O H

Carbonyl Substrate

O O

Pr-n

(80)

Et

TBDMSO

Et

TBDMSO

OH

OMe

H

(66), 88:12 d.r.

(93), 6:1 d.r.

OH

O

(84), >90:10 E:Z

(75)

Bu-n

(—), >99:1 d.r., 25:75 E:Z

t-Bu

I (66), >99:1 d.r. Toluene, rt

4 kbar, 60°, 12 h

2. I2, 110°

1. Toluene, rt, 2 d

8 kbar, 3 d

OH

OH

OH

"

O

O

Petroleum ether,

Ether, rt

Ether, rt

THF, –100°

OH

Product(s) and Yield(s) (%), % ee

I

B

O

O

B

O

O n-BuLi, B(Bu-n)3,

N

H N

Conditions

OMe

B

O

Pr-n

B(OC6H13-n)2

B(OC6H13-n)2

Bu-n

B(Bu-n)2

Allylborane Reagent

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

68

147

207

102

31

31

685

Refs.

315 S

TBDMSO

Et

TBDMSO

O

O

H

H Cl

B

O

Cl

B

O

B

O

O

B

O

B

O

OMe

B

O

O

O

Cy

O

O

O

Cy

–78° to rt

Petroleum ether,

60 h

Toluene, 0° to rt,

—

–78° to rt

Petroleum ether,

Toluene, 4 kbar, 8 h

Toluene, 4 kbar, 8 h

S

TBDMSO

Et

TBDMSO

Et

OH

OH

OH

OH

(94), 86:14 d.r.

TBDMSO

Et

OH

OH

Cl

OMe

(67), 60:6.5 d.r.

(86), 75:25 d.r.

Cl (69), >99:1 d.r.

(86)

(53), 81:19 d.r., >99:1 anti:syn

TBDMSO

Et

TBDMSO

Et

TBDMSO

676

149

694, 687

676

149

68

316

C7

C6

Ph

O

O

Et

H

O

O H

Carbonyl Substrate

Br

O

Cy Cy

Bu-n

B(Bu-n)2

SnMe3

BBN

TMS

BBN

BCy2

B

O

Allylborane Reagent

Cy2BH

Br,

N

H N O

THF, –100°

n-BuLi, B(Bu-n)3,

30 min

Base, ether, –78°,

30 min

Base, ether, –78°,

n-Bu4NBr, 0°

2. Aldehyde,

1.

Benzene, 80°, 3 d

Conditions

2 1 1

pyr pyr n-BuLi s-BuLi OH

1

Base

Br

TMS Equiv

OH

OH

O

OH

(56)

(50)

(90)

(75)

Bu-n

(84), >95:5 d.r., >90:10 E:Z

Ph

OH

>98:2

>98:2

>92:1

88:5

d.r.

(56), 15:85 E:Z

>98:2

>98:2

92:7

93:5

Z:E

(81), >96:4 d.r.

Product(s) and Yield(s) (%), % ee

SnMe3 (90), >98:2 d.r., >98:2 Z:E

Ph

Ph

Ph

O

Et

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

685

682

682

680

688, 681

Refs.

317

TMS

BCy2 BBN BBN BCy2 BCy2

Me n-Bu n-Bu n-Bu n-Bu

Cl

B

O

B

O

BCy2

Me

Cl

BBN

Me

O

BBN

Me

O

R2

R2

R1

R1

Et

BEt2

O

Neat, 0°, 15 h

Neat, 0°, 15 h

—

–100°

n-BuLi, BEt3, THF,

N

H N

Ph

Ph

Ph

Ph

III

R1

+

Ph

(82) (83) (86) (85) (79)

H2SO4 NaOH H2SO4 NaOH H2SO4

OH

Cl

(83)

NaOH

Cl

(87)

H2SO4

R1

+

(—), 92, 6:94 E:Z

0:0:3:97

0:0:97:3

1:92:2:5

92:1:4:2

0:0:8:92

0:0:97:3

1:91:2:6

92:1:5:2

I:II:III:IV

IV

R1

(82), 5:95 E:Z

(86)

OH

Ph

II

>90:10 E:Z

(67), >95:5 d.r.,

I + II + III + IV

R1

+

Et

NaOH

Work-Up

Ph

I

OH

66, 669

146, 668

684

685

318

C7

Ph

O H

Carbonyl Substrate

Ph

O

Ph

O

O

Ph

B

O

B

O

O

O

O

R

OH

Ph

O

Cy

R

OH

TMS

Br

B

B

Cl

B

O Cy

Allylborane Reagent

Neat, 0°, 15 h

Neat, rt, 15 h

Ether, rt, 24 h

Ether, rt, 24 h

THF, –78° to rt, 18 h

Conditions

Ph

Ph

Ph

Ph

Ph

OH

OH

(89), 12:88 E:Z TMS

Br

CH2CH2Ph

Cy

Ph

R

(80), 3:97 E:Z

R

OH

CH2CH2Ph

Pr-i

R

(79), >99, >79:1 Z:E

R

OH

Cl

>20:1 d.r.

OH

>14:1 d.r.

OH

OH

(83), 92

(83), 92

(65), 95

(92), 94

(88), 92

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

146

146, 668

175

175

65

Refs.

319 O

O

R

R

O

Ph Ph

B O

OMe

O

Ph

Ph OMe

Ph Ph

O

B

Ph OMe OMe

Ph

O

O

O

B

O

SiMe2Ph

B

O

TMS

B

O

"

Toluene, –100° to rt

Toluene, –100° to rt

2. I2, 110°

1. Toluene, rt, 2 d

THF , 100°, 24 h

120°, 36 h

Pyr, ether to neat,

Ether, reflux, 36 h

Ph

Ph

Ph

Ph

Ph

Ph

OH

OH

OH

OH

OH

OH

R

R

H

(92)

CH2C(O)NMe2

CH2CO2Et

R

OMe

CH2C(O)NMe2

CH2CO2Et

R

O

(89), 9:91 E:Z

(91), 22:78 E:Z

(89), 12:88 E:Z

SiMe2Ph

TMS

TMS

(91), 96

(78), >94

(89), >94

(—)

(78), >94

85

85

207

675

689

689

320

C7

Ph

O H

Carbonyl Substrate

Bu-n

B

O

Pr-i

B

O

Pr-i

B

O

Pr-i

B

O

B

O

O

O

O

O

O

Allylborane Reagent

–15°, 45 min

O i-PrMgCl, THF,

O B

–15°, 15 min

O i-PrMgCl, THF,

O B

–78° to rt

O i-PrMgCl, THF,

O B

–15°, 45 min

O n-BuMgCl, THF,

O B

2. Aldehyde, rt, 24 h

1. Cl

2. Aldehyde, 24 h

1. Cl

2. Aldehyde, rt, 24 h

1. Cl

2. Aldehyde, rt, 24 h

1. Cl

Ether, –70° to rt, 16 h

Conditions

I Pr-i

OH

OH

Pr-i

+

II

Bu-n (6), >99:1 d.r.

Ph

OH +

Pr-i

(59), 20:80 E:Z

Ph

OH

Bu-n

(52), 30:70 E:Z

Ph

OH

(55), 30:70 E:Z

(73), 23:77 E:Z

I (13), >99:1 d.r. + II (32), 30:70 E:Z

(13), >99:1 d.r.

Ph

Ph

Ph

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

87

87

87

87

148

Refs.

321

R

O

B

O

B

O

B

O

O

OPh

Cl

Cl

B

O

O

O

–78° –78° 0°

— — —

Sc(OTf)3 TfOH —

TMS TMS SiMe2Ph

24 h

Petroleum ether, rt,

CH2Cl2, 0° to rt, 15 h

12-18 h

Petroleum ether, rt,

I

Cl

Ph

OH

(26)

(11)

(22)

(43)

(40)

(46)

(24)

(50)

(75)

(99)

(63)

(75)

(53-73), 96-98, 95:5 d.r.

40 h

40 h

15 h

40 h

40 h

15 h

40 h

40 h

15 h

40 h

40 h

15 h

Time

OPh

(63), 5:95 E:Z

I (53-73), 95:5 d.r., 5:95 E:Z

Ph

OH

–78°

0°

—

—

TMS

–78°

–78°

4 Å MS

TfOH

Br

—

–78°

4 Å MS

Sc(OTf)3

Br

—

0°

4 Å MS

—

Br

TfOH

–78°

4 Å MS

TfOH

Et

Sc(OTf)3

–78°

4 Å MS

Sc(OTf)3

Et

SiMe2Ph

0°

4 Å MS

—

SiMe2Ph

Temp

Additive

Catalyst

R

Et

Ph

OH

R

additive, CH2Cl2

Catalyst (10 mol%),

4:1

4:1

1:6.2

3:1

4:1

1:6.7

9:1

10:1

13:1

1:1.7

1:1.3

2:1

E:Z

68

67

83, 67

690

322

C7

Ph

O H

Carbonyl Substrate

Me

Me

O

O

O

Cl

B

O

B

O

TMS

B

O

O

O

O

SO2Me

B

O

Ts

B

TMS

N

N

TBDMSO B

O O

Allylborane Reagent

CH2Cl2, rt, 20 h

120°, 36 h

Pyr, ether to neat,

16 h

Ether to neat, 125°,

2. H+, MeOH

1. 4 kbar, rt, 3 d

4 kbar, rt, 3 d

Neat, rt, 10 h

Conditions

OH

Ph

Ph

Ph

OH

OH

OH

MeO

Ph

Ph

OH

O

(—), 96:4 E:Z

(95), 94:6 d.r.

TMS

(—), 90:10 E:Z

(56), 99:1 d.r.

(64), 99:1 d.r.

(55)

Ts

TMS

Ph

N

Me

OTBDMS

Cl

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

676

689

689

672

672

67

Refs.

323 R

R

R

TBDMSO Cl

O

Ph Ph

B

B

O O

CO2Et

O

OMe

O

Ph

CO2Et Ph OMe

Ph Ph

O

B

Ph OMe

B

O

OMe

Ph

O

O

"

OMe

B

O

Toluene, 60°, 12 h

CH2Cl2, rt

CH2Cl2, rt

Neat, rt, 10 h

20°, 60 h

–78° to rt, 2 d

Petroleum ether, I OMe

(79), 90

Ph

Ph

Ph

Ph

OH

R

OH

R

OH

TBDMSO

OH

R

Cl

(78), >99

(90), >98

(65), >99

(95), >98

(57), 83 (46), 84 (59), 85

Cy Ph t-Bu

(28), 85

1:3

9:1

1:2

1:3

1:4 n-Bu

E:Z Me

(51), 84

Ph

Me

R

Ph

Me

R

R

CO2Et

CO2Et

(55)

I (65), 90, >95:5 Z:E

Ph

OH

691

86

86

67

147

68

324

C7

Ph

O H

Carbonyl Substrate

n-Pr

O

B

O

B

TMS

Cl

Cl

B

O

B

O

B

O

O

O

O

O

O

O

Cy Cy

SiMe2Ph

B

O

Allylborane Reagent

16 h

Ether to neat, 125°,

CH2Cl2, 0° to rt, 15 h

CH2Cl2, 0° to rt, 15 h

Petroleum ether, 12 h

–78° to rt

Petroleum ether,

—

Conditions

Ph

Ph

Ph

Ph

Ph

Ph

OH

OH

OH

OH

OH

OH

Pr-n

(56), 96:4 d.r., 93:3 E:Z

(56), 97, 96:4 d.r.

TMS

(—), 13:87 E:Z

Cl

Cl

(71), 99

(95), 94:6 d.r.

SiMe2Ph

(89), 9:91 E:Z

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

689

67

67

64, 63

676

675

Refs.

325

O

O

B

O

B

O

B

O

O

O

SiMe2Ph

Bu-n

n-Bu

Pr-n

B

O

O

O

R

O B

B

O

O

O

2

B ,

P NMe2,

Pd2(dba)3, 22°, 10 h

O

O

R,

O

Ar Ar

Ar Ar O

Neat, rt, 5-8 d

Neat, rt, 5-8 d

Ether, –78°

Ar = 3,5-Me2C6H3

3. NaOH, H2O2

2. Aldehyde, 22°, 14 h

1.

—

Ph

Ph

Ph

Ph

Ph

OH

OH

OH

OH

OH

Bu-n

Bu-n

O

Pr-n

R

(83), 84

(83), >99:1 d.r.

(72), >99:1 d.r.

(42), 97:3 d.r.

Cy

(96), 87

(81), 93

(46), 94:6 E:Z

n-C10H21

Ph

R

SiMe2Ph

673

673

22

187

675

326

C7

R

Ph

O H

O H

Carbonyl Substrate

i-Pr

Et

B

HO

Cy

Cy

B

O

B–Et2SePh

HO

n-C5H11

R

B

O

Ipc-(–)

Ipc-(–)

Allylborane Reagent

, LDA,

2. Et3B, –78° to 0°, 1 h

THF, –78°, 30 min

1. PhSe

THF, –15° to 5°

THF, –15° to 5°

CH2Cl2, rt, 18 h

Conditions

R

Ph

Ph

Ph R

5:95 4:96

(65) (88)

t-Bu Ph

(88) (80) (65)

MeO O2N

Cy

H

I

OH

5:95 (77)

77:23

71:29

94:6

I:II

R

+

Et

—

—

86:14

E:Z

II

OH

(70), 60, 99:1 d.r.

Et

Ipc-(–) (72), 79, 98:2 d.r.

6:94

(72)

I + II

Pr-i

E:Z

Refs.

692

674

674

6:94 677 5:95

(86) (82)

Cl

n-C5H11

R

R

OH

C5H11-n

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

327

Cy

O

Si

OH

i-Pr

R

H

O

Pr-i

O

H

H

O

O

H

Br

O

Ts

N

O

BCy2

"

B Ph

C5H11-n

B

O

N(Pr-i)2

O

N B

Pr-n OH

O

Ts

Cy2BH

Br,

n-Bu4NBr, 0°

2. Aldehyde,

1.

2. HF•pyr, pyr, THF

1. Toluene, 80°

Toluene, 80°

CH2Cl2, rt, 18 h

Toluene, 60°, 48 h

Cy

HO

HO

OH

OH

O

Pr-i

HO

Si

OH

i-Pr

R

OH

Br

Pr-n

OH Ph

(63), 14:86 E:Z

Pr-n

Ph

(—)

(—)

OH

(35), 1:9 E:Z

>95:5

(74), 84

p-Br

C5H11-n

>95:5

(66), 85

p-MeO

Z:E 95:5

(87), 84

N(Pr-i)2

O

H

R

O

680

236

236

677

51

328

C7

Cy

O H

Carbonyl Substrate

Ph

Ph

Ph

Ph

O B

–15°, time 1

PhMgCl, THF,

Cl

O B

–78° to rt

PhMgCl, THF,

Cl

O B

B O

O

O

O B

–15°, 30 min

PhMgCl, THF,

Cl

O

2. Aldehyde, rt, 24 h

1.

2. Aldehyde, rt, 24 h

–15°, 45 min

PhMgCl, THF,

1.

2. Aldehyde, 24 h

1.

B

O

O

O

2. Aldehyde, rt, 24 h

1.

2. Aldehyde, 24 h

–78° to rt

PhMgCl, THF,

O B

Cl O

O

O

1. Cl

Conditions

O

B

O

"

B

O

Allylborane Reagent

I Ph

30 min

15 min

Time 1

II

d.r. 98:2 >99:1

I (34)

(15)

(41)

II

II (60), 2:98 E:Z

I (21), >99:1 d.r. + II (21), 2:98 E:Z

98:2

2:98

E:Z

Ph (39), 2:98 E:Z

Cy

(17)

+

OH

I (8), >99:1 d.r. + II (32), 98:2 E:Z

I + II

(9), >99:1 d.r.

Cy

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

87

87

87

87

87

Refs.

329

MeO

O

n-C6H13

O H

O H

Ph Ph

O Ph

B

O

B

O O

OMe

B

O

O

O

Cy

O

BCy2

Ph

O

OH

TMS

Br

B

Ph

B

O

Cy

–15°, 30 min

O PhMgCl, THF,

O B

Cy2BH

Br,

—

20°, 60 h

36 h

Ether to neat, 130°,

n-Bu4NBr, 0°

2. Aldehyde,

1.

Ether, rt, 24 h

2. Aldehyde, rt, 24 h

1. Cl

O

n-C6H13

n-C6H13

n-C6H13

MeO

OH

Ph

OH

OH

OH

OH

OMe

TMS

Br

(91), 94, >14:1 d.r.

OH

OH

(67)

(87), 88, >95:5 Z:E

(80), 33:67 E:Z

(55), 12:88 E:Z

(67), 20

64

147

689

680

175

87

330

C8

C7

Ph

O

MeO

O

O

O

H

H

O H

O H

Carbonyl Substrate

O

O

O

Ts B

N

Cy

Bu-n

B(Bu-n)2

Ts

N

C5H11-n

B

O

N(Pr-i)2

Et

O

Cy

B–Et2SePh

B

O

Allylborane Reagent

,

THF, –100°

O N n-BuLi, B(Bu-n)3,

H N

Toluene, 60°, 48 h

CH2Cl2, rt, 18 h

2. Et3B, –78° to 0°, 1 h

30 min

LDA, THF, –78˚,

1. PhSe

rt, 7 d

Conditions

Ph

OH

I

OH

OH

H

O

Et

O

+

I:II >99:1

I + II (90),

>90:10 E:Z

(75), >95:5 d.r.,

>95:5 Z:E

(69), 85,

(87), 5:95 E:Z

N(Pr-i)2

Bu-n

O

C5H11-n

II

OH

Et

(80), 97.5:2.5 d.r.

Product(s) and Yield(s) (%), % ee

OH

O

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

685

51

677

692

693

Refs.

331

C9

Ph

MeO

O H

OMe OBn O H O

B

O

O

B O

TMS

O

Cy

O

BBN

BCy2

Pr-i

Br

Cl

B

O

B

O

Cy

Cy2BH

Br,

–15°, 45 min

O i-PrMgCl, THF,

O B

2. Aldehyde, rt, 24 h

1. Cl

30 min

Pyr, ether, –78°,

n-Bu4NBr, 0°

2. Aldehyde,

1.

3d

Petroleum ether, rt,

8 kbar, 3 d

Petroleum ether,

8 kbar, 3 d

Petroleum ether,

Ph

Ph

Ph

MeO

Ph

Ph

OH

OH

OH

OH

OH

(85)

Pr-i

102

102

87

682

680

(95), 4:1 d.r. 53

(60), 30:70 E:Z

TMS

Br

Cl

(65), 18:82 E:Z

OMe OBn OH

(—), 95:5 d.r., 30:70 E:Z

(—), 98:2 d.r., 6:94 E:Z

332

C9

Ph

Ph

O

O

H

H

Carbonyl Substrate

Ph

O

Ph

O

B

B

O

Ph

B

O O

C5H11-n

O

R

OH

Ph

O

R

OH

Et

BEt2

C5H11-n

B

O

Allylborane Reagent

CH2Cl2, rt, 18 h

Ether, rt, 24 h

Ether, rt, 24 h

THF, –100°

O N n-BuLi, BEt3,

H N

CH2Cl2, rt, 18 h

Conditions

Ph

Ph

Ph

Ph

Ph

OH (75), 5:95 E:Z C5H11-n

50:1 (69), 92 i-Pr

d.r. >20:1 (87), 91

R Ph

R

>14:1

(95), 95

OH

>14:1

(95), 95

R d.r.

OH

>90:10 E:Z

Et (52), 97:3 d.r.,

i-Pr

OH

(77), 91:9 Z:E C5H11-n

Ph

R

OH

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

677

175

175

685

677

Refs.

333

O

O

Et

Et

O

TBDMSO

Et

`

Et

O

H

H

H

PMB O

PMB O

O

H

PMB O O

O

PMBO

n-C6H13

O

H

O

B

O

O

B

O

Cl

O

B

O

"

OMe

B

O

OMe

B

O

Cy

O

O

O

Cy

C5H11-n

B

O

Cy

Cy

2d

Petroleum ether, rt,

60 h

4 Å MS, toluene, rt,

4 kbar, 20°

60 h

4 Å MS, toluene, rt,

Toluene, 4 kbar, 12 h

4 kbar, rt, 3 d

Petroleum ether,

CH2Cl2, rt, 18 h

O

I

O

O

Et

Et

O

TBDMSO

PMB OH

PMB OH

OH

O

PMB OH

(56), >99:1 d.r.

PMB O OH

(85), 1:9 E:Z 677

149, 197

147

197

(79), >95:5 d.r. 688, 681

Cl

OMe

OMe

(60-85), 75:25 d.r. 628

(95), 80:16 d.r. 681

C5H11-n

(60-85), 75:25 d.r.

O

I (65), 77:23 d.r.

Et

TBDMSO

Et

Et

PMBO

n-C6H13

OH

334

C11

C10

i-Pr

O

O

O

OH

3

H

OH

H

O

O

O

2

H

H

O H

Carbonyl Substrate

O

O

TMS

O

O

O

B

O

B

O

B

O

B

O

B

O

O

O

O

O

Cy

Cy

Cy

Cy

Allylborane Reagent

Ether, reflux, 16 h

(10 mol%), 10 kbar

2-Hydroxypyridine

2. I2, 110°

1. Toluene, rt, 2 d

2. I2, 110°

1. Toluene, rt, 2 d

4 kbar, 12 h

Conditions

i-Pr

OH

H

O

HO

OH

O

3

2

OH

2

O H

2

H

(71)

O

(35)

(35), 63:27 d.r.

(63), 16:84 E:Z

TMS

OH

(82)

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

689

694, 687

207

207

693

Refs.

335

C13

C12

Ph

Ph

OH

Et

3

TBDMSO

O

2

H

O

O H

OH

O

O

O

N B

O

O

B

O

B

O

B

O

O

O

O

N(Pr-i)2

O

Ts

Cy Cy

Ts

N

2. I2, 110°

1. Toluene, rt, 2 d

2. I2, 110°

1. Toluene, rt, 2 d

(10 mol%), 10 kbar

2-Hydroxypyridine

Toluene, 60°, 48 h

Ph

OH

Et

3

TBDMSO

Ph

O

OH

2

OH

2

O H

2

H

(40)

O

OH

N(Pr-i)2

O

(100), 94:6 d.r.

OH

(67), 85, >95:5 Z:E

OH

(80)

207

207

694, 687

51

336

C18

C15

C14

C13

Ph

H

O

O

Et

Et

R=

O

O

O

5

O

O

O

O

R

O

PMP

O

PMP

O H

OBn OTBDMS

O

O

OH

PMBO

O

Carbonyl Substrate

H

O B

O

B

O

Cl

TBDMSO

O

O

B

O

Cy

Cy

O

OTBDMS

Cy

Cy

TBDMSO

B O

OH O

Allylborane Reagent

3d

Petroleum ether, 10 kbar,

3d

Petroleum ether, 10 kbar,

4d

Petroleum ether, rt,

48 h

CH2Cl2, –78° to rt,

Conditions

Ph

O

O

Et

Et

O

O

TBDMSO

O

O

OH

O

R (55)

OH

OH

(53)

OH

Cl

OTBDMS

PMBO

(70), 89:11 d.r.

O

PMP

(79), >95:5 d.r.

O

PMP

OH

O

OTBDMS

5

OH O

O

Product(s) and Yield(s) (%), % ee

TABLE 4. ADDITION OF α-SUBSTITUTED REAGENTS (Continued)

688, 696

688, 696

695, 208

202

Refs.

337

C20

Ph

TBDMSO

O H O O

B

O O 2. I2, 110°

1. Toluene, rt, 2 d

Ph

(69), 9:1 E:Z

TBDMSO

OH

H

O

208

338

C2

O

H

Carbonyl Substrate

N3

B

B

O O

O

Ph

B[(–)-Ipc]2

BBN

B(Pr-n)2

B[(+)-Ipc]2

B

O

3

B(Pr-n)2

Allylborane Reagent

Hexane, –40°

Ether, 0°, 1 h

THF, ether, –78°, 1 h

THF, ether, –78°, 1 h

–70° to rt

Ether, –78° to rt

Neat, 0-20°

Neat, 0-20°

Conditions

OH

OH

OH

I (65)

I

OH

OH

I (93)

I

OH

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS

N3

(82), 74

(75)

(65), 90

(84)

(56), 90

(92)

Product(s) and Yield(s) (%), % ee

122, 244

701

699, 700

699

698

697, 136a

238

238

Refs.

339

C3

O

EtO

H

RO

O

O

O

H

H

H

H

O

O

Ph

O Ph

B[(+)-Ipc]2

B

O

B(OMe)2

B(OMe)2

B(2-d-Icr)2

OPh

MeO2C

B

O B O

O

N

O S O

THF, –78° a

Ether, –78° to rt

rt, 7 d

MeOH, 0° to rt, 15 h

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

Ether, –78°

EtO

RO

OH

H

H

OH

OH

OH

O

OH

OPh

(75), 70 (47), 63

pentane

(60), 72

(57), 92

(67), 42 CH2Cl2

(86), 77

(67), 78

(70), 97

(90), 95

THF

ether

toluene

Solvent

Bn

TBDMS

R

(34)

CO2Me

OH

OH

(69), 84

704

697, 136a

703

702

27

246

340

C3

O

O H

Carbonyl Substrate

MeO2C Ph

Ph

O

B(Pr-n)2

3

O

O

B

O

B

B

[(+)-Ipc]2B

B(2-d-Icr)2

OPh

B[(+)-Ipc]2

B[(+)-Ipc] 2

Allylborane Reagent

Neat, 0-20°

Neat, 0-20°

Hexane, –40°

rt, 7 d

Ether, –78° a

THF, –78° a

Ether, –78° to rt

Conditions

I (94)

I

OH

OH

OH

(100), 68 (99), 67 neat

(90)

(95), 70

(99), 78 pentane

ether

toluene

(85), 70

CO2Me

Solvent

(67), 76

OH

OPh

(54), 90

(45), >95, 93:7 d.r.

OH

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

238

238

122, 244

703

176, 705

704

697, 136a

Refs.

341

RO

CF3

O

CF3

H

R = TBDPS

R = THP

O

Ph

O B O

[(+)-Ipc]2B

B

B(Pr-n)2

B(Pr-n)2

B(Pr-n)2

B(Pr-n)2

BBN

B

B[(+)-Ipc] 2

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

Ether, –78° a

Neat, 0-20°

Neat, 0-20°

–70° to rt

Ether, –70° to rt

Pentane, rt, 2 h

Neat, 0-20°

I

RO

RO

I (86)

CF3

CF3 OH

OH

HO

I (95)

I (91)

OH

OH

(89)

(94)

OR

(73)

(77), 97

OH

OH

(45)

27

176

238

238

698

706, 702

103

238

342

C3

O

O

PMBO

O H

O H

Carbonyl Substrate

R=

N

O

Ether, –78° a

O

O

O

O

THF, –78°, 3 h

Ether, –78°

Ether, –78°

O

O

O

O

O

Ph SnBu3, N PMBO Ph, Br B N Ts CH2Cl2, –78°, 1.5 h Ts

a B[(–)-Ipc] 2 Ether, –78°

Ts

N

Ph

[(–)-Ipc] 2B

B

TBDMSO R

B[(+)-Ipc] 2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

S

S

Ts

Ph

Conditions

[(+)-Ipc]2B

TMS

R

TBDMSO

Allylborane Reagent

TMS

OH

OH

(50), 160:22:1 d.r.

OH

O

O

O

O

(31), 85:15 d.r.

(—), 97:3 d.r.

(—)

(38), 66:14.5:1 d.r.

OH

OH

OH

OH

R

OTBDMS

(100), 11:1 d.r.

OH

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

176, 705

176, 705

707

571

571

191

Refs.

343

C4

n-Pr

O H

O

TBDPSO

H

O H

R

R

N3

Br

R=

R=

S

Ts

S

Ts

O

N

B

B[(+)-Ipc]2

B

O

B(OPh)2

S

S

N

B

Ph

N

Ph

Ts

N

Ts

Ph

Ph Ph,

Ph BBr3, CH2Cl2

Ts

Ts HN H N

SnBu3,

SnBu3,

Ph,

Ph BBr3, CH2Cl2

Ts

Ts HN H N

Ether, –78° to rt

Ether, 0°, 1 h

THF, 0° to rt, 18 h

2. Aldehyde, –78°, 1 h

1.

R

2. Aldehyde, –78°, 1 h

1.

R

n-Pr

OH

OH

OH

TBDPSO

TBDPSO

N3

Br

(56), 91

(64)

(85)

(80), 4:1 d.r.

OH

(85), 7.7:1 d.r.

OH

R

R

697, 136a

701

709

708

708

344

C4

i-Pr

n-Pr

O

O

H

H

Carbonyl Substrate

Ph

B[(+)-Ipc]2

B[(–)-Ipc]2

B

B

[(+)-Ipc] 2B

TMS

O

BBN

B

O

B(2-d-Icr)2

OPh

Ether, –78° to rt

1h

THF, hexane, –78°,

Ether, –100°, 3 h

Ether, –100°, 3 h

1h

THF, hexane, –78°,

Hexane, –40°

Ether, –78° a

Conditions

a B[(+)-Ipc]2 Ether, –78°

Allylborane Reagent

I

OH

OH

OH

i-Pr

i-Pr

i-Pr

OH

OH

OH

I (80), 27

i-Pr

i-Pr

n-Pr

n-Pr

OH

Pr-i

(41), >95, 93:7 d.r.

(57), 96

(65), 92

(78), 81

(65)

(84), 65

(78), 74

OH

OPh

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

176, 705

697, 136a

699

141

141

699

122, 244

704

Refs.

345 O

TBDMSO

N H

O

O H

O Ph

3

B

B

O

B

O

O

B

Ph

B[(–)-Ipc] 2

SO2Ph

N

Ph

O

B(OPh)2

O

PhO2S N Bu3Sn

MeO2C

N3

Br

B

[(–)-Ipc]2B

CH2Cl2, –78°, 2-3 h

THF, reflux, 2 h

Neat, rt, 9 d

Ether, 0°, 1 h

THF, 0° to rt, 18 h

Hexane, –40°

Ether, –78° a

OH

OH

OH

OH

TBDMSO

N H

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

OH

(80)

(71)

(80)

OH

(85), 3.2:1 d.r.

O

(91)

CO2Me

N3

Br

Pr-i

SnBu3

(38), >95, 91:9 d.r.

(87), 76

OH

710

294

57

701

709

122, 244

176, 705

346

C4

TBDPSO

O H

Carbonyl Substrate

R

R

R

Ts

S

N

B

S

S

N

Ph

Ts

Ts

N

B

Ph

Ph

Ph

N

Ts

N

R = (CH2)3OTBDPS

OBz

R=

R=

S

Ts

N

B

Ts

Allylborane Reagent

Ph

Ph

Ts HN H N

SnBu3,

Ph,

Ph BBr3, CH2Cl2

Ts

R

Ts HN H N

SnBu3,

Ph,

Ph BBr3, CH2Cl2

Ts

R

Ts HN H N

OBz

Ph,

SnBu3,

2. Aldehyde, –78°, 1 h

Ph BBr3, CH2Cl2

Ts

1. R

2. Aldehyde, –78°, 1 h

1.

2. Aldehyde, –78°, 1 h

1.

Conditions

TBDPSO

I (80), 4:1 d.r.

TBDPSO

R OBz (56), >20:1 d.r.

OH

I (77), 15:1 d.r.

OH

R

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

708

708

708

Refs.

347

TBDPSO

O H

R

R

R

R=

S

S

OBz

S

OTBDMS

R=

R=

S

N

B

N

B

N

Ts

Ts

Ts

B

Ph

Ph

Ts

Ph

N

N

Ts

N

Ts

Ph

Ph

Ph

SnBu3,

Ph,

Ph BBr3, CH2Cl2

Ts

Ts HN H N

Ts HN H N

SnBu3,

Ph,

Ph BBr3, CH2Cl2

Ts

R

Ts HN H N

Ph,

OTBDMS Bu3Sn

OBz

2. Aldehyde, –78°, 1 h

Ph BBr3, CH2Cl2

Ts

1. R

2. Aldehyde, –78°, 1 h

1.

2. Aldehyde, –78°, 1 h

1.

R

,

TBDPSO

TBDPSO

TBDPSO

OBz (56), >25:1 d.r.

OH

(76), 1.7:1 d.r.

OH

(75), 5.4:1 d.r.

OH

R

OTBDMS

R

R

708

708

708

348

C5

C4

O

O

PMBO

O H

THPO

TBDPSO

O

O

H

H

Carbonyl Substrate

N

B

N

Ph

Ts

B(Pr-n)2

B[(–)-Ipc]2

BBN

B(Pr-n)2

B(Pr-n)2

Ph

B[(+)-Ipc] 2

R = (CH2)3OTBDPS

Ts

[(+)-Ipc]2B

R

OBz

Allylborane Reagent

Ts HN H N

OBz

Ph,

SnBu3,

THF, ether, –78°, 1 h

THF, ether, –78°, 1 h

–70° to rt

Ether, –70° to rt

Ether, –78° a

2. Aldehyde, –78°, 1 h

Ph BBr3, CH2Cl2

Ts

1. R

Conditions

I (60)

PMBO

OH

I

OH

THPO

TBDPSO

OH

OH

OH

R

OH

OBz

(60), 96

(96)

(50)

(48)

(83), >20:1 d.r.

OH

PMBO

OTHP

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

699, 700

699

698

702

176

708

Refs.

349

t-Bu

O H

B

O

B

O

O Ph

B

O O Ph

Hexane, –40°

Ether, –78° to rt

rt, 8 d

rt, 8 d

OCH(Pr-i) 2 4 Å MS, toluene, –78°, 1h O

OCH(Pr-i)2

Ph

THF, ether, –78°, 1 h

OCH(Pr-i) 2 4 Å MS, toluene, –78°, 1h O

OCH(Pr-i)2

B[(+)-Ipc]2

B

CO2Me O

B

O

O

O

O

CO2Me O

Br

Br

O

B[(+)-Ipc]2

t-Bu

t-Bu

OH

OH

OH

OH

OH

OH

OH

(82), 88

(—), 20

(98), 88

(93), 87

(92), 70

(55), 90

CO2Me

CO2Me

Br

Br

(60), 96

122, 244

697, 136a

713

713

711, 712

711, 712

699, 700

350

C5

i-Pr

t-Bu

O

O

H

H

Carbonyl Substrate

O

B

B[(–)-Ipc]2

B[(+)-Ipc]2

BBN

B(Pr-n)2

B

O

[(+)-Ipc]2B

N3

O

N

O S O

B[(+)-Ipc]2

Allylborane Reagent

Ether, –78° a

THF, ether, –78°, 1 h

THF, ether, –78°, 1 h

THF, ether, –78°, 1 h

–70° to 0°

Ether, 0°, 1 h

Ether, –78°

Conditions

i-Pr

i-Pr

i-Pr

I (65)

i-Pr

t-Bu

t-Bu

N3

OH Pr-i

(60), 94

(65), 96

(94)

(68)

(89), 91

(53), >95, 93:7 d.r.

OH

OH

OH

I

OH

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

176, 705

699, 700

699, 700

699

698

701

246

Refs.

351

n-Bu

O H

B

O

B

O

O

B

O O

O

n

OCH(Pr-i)2

OCH(Pr-i)2

O

OCH(Pr-i)2

OCH(Pr-i)2

Ph

Ph

Ph

O B O

B

CO2Me O

B

O

O

O

O

CO2Me O

Br

Br

O

CH2Cl2, rt; H2O, 1 h

CH2Cl2, –78°, 16 h

Sc(OTf)3 (10 mol%),

rt, 8 d

rt, 8 d

–78°, 1 h

4 Å MS, toluene,

–78°, 1 h

4 Å MS, toluene,

n-Bu

n-Bu

i-Pr

i-Pr

i-Pr

i-Pr

OH

OH

OH

OH

OH

OH

(—), 82

(68)

(89), 98

CO2Me

(—), 25

(90), 93

(83), 90

CO2Me

Br

Br

234

28

713

713

711, 712

711, 712

352

C5

O

O

OH

PMBO

Et

O

O

O

OEt

H

N

H

O

O

O H

Carbonyl Substrate

B

O

OPiv

PhO2S

O

B(OPh)2

B(OH)2

B(OPh)2

TBDMSO

Br

Br

B(Pr-n)2

B(Pr-n)2

B(Pr-n)2

B

N

Ph

CH2Cl2, rt; H2O, 2 h

THF, 0° to rt, 18 h

—

THF, 0° to rt, 18 h

Ether, –70° to rt

Neat, 0-20°

Conditions

Ph CH2Cl2, –78°, 2-3 h SO2Ph

N

n

Allylborane Reagent

O

O

OH

PMBO

O

Et

HO

HO

HO

OH

O

N

OH

Br

Br

(87)

I OPiv

OTBDMS

(92), >20:1 d.r.

OH

(46)

(64), 54:46 d.r.

OH

(80)

(80)

(82)

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

710, 715

234

709

714

709

706, 702

238

Refs.

353

C6

n-C5H11

O H

Ts

PhO2S

[(+)-Ipc]2B

B[(–)-Ipc]2

SiMe2R

OPiv

TBDMSO

OPiv

TBDMSO

OPiv

TBDMSO

Ts N

Ts

N

Ph

Ph

SnBu3,

Ph, N Ts CH2Cl2, –78°

OPiv Ts N Br B

TBDMS

Ph

SnBu3,

Ether, –78° a

THF, –78°, 3 h

Ph, N Ts CH2Cl2, –78°

Ph

TBDMS

OPiv Ts N Br B

O

Ph CH2Cl2, –78°, 2-3 h

SO2Ph

N

Ph

Ts

N

Ph

B[(+)-Ipc]2

B

N

B

N

B

Ph

O

O

n-C5H11

n-C5H11

I

Ph

Me

R

C5H11-n

OH

SiMe2R

(43), 30

(62), 28

OPiv

OTBDMS

(98), >20:1 d.r.

OH

(43), >95, 92:8 d.r.

OH

OH

I (98), >20:1 d.r.

PMBO

N

I (98), >20:1 d.r.

176, 705

707

708

710

708

354

C6

n-C5H11

O H

Carbonyl Substrate

Cl

Br

Br

Br

Br

Ts

Ts

Ts

B

N

B

N

B

O

B

O

B

N

Ph

Ts

N

Ph

Ts

N

O

O

O

O

Ts

N

Ph

B(OPh)2

Ph

Ph

O

OCH(Pr-i)2

OCH(Pr-i)2

O

OCH(Pr-i)2

OCH(Pr-i)2

Ph

Allylborane Reagent

CH2Cl2, –78°, 2.5 h

CH2Cl2, –78°, 2.5 h

–78°, 1 h

4 Å MS, toluene,

–78°, 1 h

4 Å MS, toluene,

CH2Cl2, –78°, 2.5 h

THF, 0° to rt, 18 h

Conditions

n-C5H11

n-C5H11

n-C5H11

I (86), 88

n-C5H11

n-C5H11

OH

OH

OH

I

OH

OH

Cl

Br

Br

Br

(79), 88

(77), 99

(78), 92

(71), 94

(87)

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

50

50

712

712

50

709

Refs.

355

N H

OH

PivO

Et

O

O

O

O

O

H OTBDPS

O

B(Pr-n)2

B

Ts

N

B

OTBDMS

3

N

Ph

Ts

B(OH)2

B(OMe)2

B(OMe)2

B(Pr-n)2

Ph

Ph,

SnBu3,

Ph BBr3, CH2Cl2

Ts

Ts HN H N

OTBDMS

2. Aldehyde, –78°, 1 h

1.

THF, reflux, 2 h

—

MeOH, 0° to rt, 15 h

Ether, –70° to rt

N H

OH

PivO

Et

HO

OH

OH

OTBDPS

OH

(84)

OTBDMS

(70), 60:40 d.r.

(96), 7.2:1 d.r.

OH

(40)

OH (58)

716, 717

294

714

702

706, 702

356

C6

PivO

H OTBDPS

O

Carbonyl Substrate

Ts TBDPS

O

Ts TBDPS

O

Ts TBDPS

O

N

B

N

B

N

B

Ph

Ph

N

Ph

Ts

N

Ts

N

Ts

Ph

Ph

Ph

Allylborane Reagent

Ph,

SnBu3,

Ph BBr3, CH2Cl2

Ts

HN H N

O TBDPS Ts

Ph,

SnBu3,

Ph BBr3, CH2Cl2

Ts

HN H N

O TBDPS Ts

Ts

HN H N

O TBDPS Ts Ph,

SnBu3,

Ph BBr3, CH2Cl2 2. Aldehyde, –78°, 1 h

1.

2. Aldehyde, –78°, 1 h

1.

2. Aldehyde, –78°, 1 h

1.

Conditions

PivO

OTBDPS

OTBDPS I (60), 7:1 d.r.

OH

I (80), 1.2:1 d.r.

I (70), 4:1 d.r.

PivO

OH

OTBDPS

OTBDPS

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

708

708

708

Refs.

357 R

R

R=

R=

S

S

Ts TBDPS

O

S

S

N

B

Ts

Ts

N

B

N

B

Ph

Ts N

Ph

N

Ph

Ts

N

Ts

Ph

Ph

Ph

Ph BBr3, CH2Cl2

Ts

HN H N

O TBDPS Ts Ph,

SnBu3,

Ts HN H N

SnBu3,

Ph,

Ph BBr3, CH2Cl2

Ts

R

SnBu3,

Ph, Ph BBr3, CH2Cl2

Ts

Ts HN H N

2. Aldehyde, –78°, 1 h

1.

R

2. Aldehyde, –78°, 1 h

1.

2. Aldehyde, –78°, 1 h

1.

OTBDPS

OH

I (82), 4.2:1 d.r.

I (82), 1.5:1 d.r.

PivO

I (77), 1.4:1 d.r.

R

708

708

708

358

C6

N

N

PMBO

O

O

H

H

O

O H

Carbonyl Substrate

TMS

TBDPSO

Ts

PhO2S

B[(–)-Ipc]2

OMe

OPiv

TBDMSO

OPiv

TBDMSO

Ts

B

N

B

N

B

N

Ph

Ph

Ph

SO2Ph

N

Ph

Ts

N

Ph

Ts

N

Ph

Allylborane Reagent

N B

SnBu3,

N B

SnBu3,

THF, –78°, 3 h

CH2Cl2, –78°, 2-3 h

Ph, N Ts CH2Cl2, –78°

Br

Ts

Ph

TBDMS

OPiv

O

Ph, N Ts CH2Cl2, –78°

Br

Ts

Ph

TBDMS

OPiv

O

Conditions

N

N

PMBO

PMBO

OH

OH

O

O

TMS

OMe

(36), 54

(55), >20:1 d.r.

OTBDPS

OPiv

OTBDMS

(98), >25:1 d.r.

OH

OPiv

OTBDMS

(98), >25:1 d.r.

OH

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

707

710

716

716

Refs.

359

Ph

O H

3

B

B(Pr-n)2

O B(2-d-Icr)2

Ph

B(2-d-Icr)2

OPh

[(+)-Ipc]2B

"

BEt2

B[(+)-Ipc]2

OCOPh,

Ether, –78° a

–78°

a

Ether, –78° a

Neat, 0-20°

Neat, 0-20°

Et3N, THF, rt, 20 h

BEt3, Pd(PPh3)4,

OCOPh,

40°, 4 h

THF, rt, 9 h;

BEt3, Pd(PPh3)4, I

I

Ph

Ph

Ph

OH

OH

OH

I (78)

Ph

OH

I (63)

Ph

OH

O

OPh

OH

(89)

(60)

Ph

ether

THF

(39), 91

(74), 88

(72), 84

(55), >95, 84:16 d.r.

Solvent

Ph

704

704

176, 705

238

238

483

483

360

C7

Ph

O H

Carbonyl Substrate

O

B

B

O O

Ph

O B O

O

N

O S O

B

O

Ph

B[(–)-Ipc]2

BBN

Allylborane Reagent

O B O

Hexane, –40°

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

Ether, –78°

Cl

Li,

THF, ether, –78°, 1 h

THF, ether, –78°, 1 h

Conditions

I

OH

OH

OH

Ph

OH

I (64), 98

Ph

Ph

Ph

Ph

OH

(83), 40

(92), 89

(80)

(60), 93

(60)

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

122

27

246

52

699

699

Refs.

361 B

Br

N3

O

MeO2C

O

B

O

B

O

B

O

O

O

O

O

B

O

B(OPh)2

B

O

O

(EtO)3C

MeO2C

O B

Li,

2

,

50°, 16 h

allene, dioxane,

O B O

O

THF, 0° to rt, 18 h

Ether, 0°, 1 h

90°, 16 h

KOH (aq), dioxane,

2. PhI, PdCl2(dppf),

1.

Neat, rt, 14 d

Cl

(EtO)3C

Neat, rt, 6 d

Ph

Ph

Ph

Ph

Ph

Ph

OH

OH

OH

OH

OH

OH

Br

N3

Ph

(70), 10

(56)

(98)

(89)

(70)

(75)

CO2Me

C(OEt)3

CO2Me

709

701

718

58

52

57

362

C7

R

1

Ph H

O

R1

H

= H, MeO, O2N

R1 = H, O2N

O

Carbonyl Substrate

O

O

O

Ph

Ph

B

O O

O

n

OCH(Pr-i)2

OCH(Pr-i)2

O

OR

OR

B[(–)-Ipc]2

Ts

N

N B

Ts

B

O

B

O

SiMe2R2

R

Br

Br

O

Allylborane Reagent

CH2Cl2, H2O, rt

THF, –78°, 3 h

CH2Cl2, –78°, 2.5 h

–78°, 1 h

4 Å MS, toluene,

–78°, 1 h

4 Å MS, toluene,

Conditions

R1

R1

Ph

Ph

Ph

OH

OH

OH

R

Br

Br

Me

O2N

O2 N

(98), 84

(97), 47

(92), 47

3h

5h

2h

Time

(72), 33

(63), 22

(46), 75

MeO

H

R1

Ph

H

OH

Me

R2

SiMe2R2

(79), 84

(73), 79

H

R1

OH

Cl

Br

R

(98), 84

CH(Pr-i)2

Pr-i

Et

R

(96)

(95)

(87)

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

234

707

50

712

712

Refs.

363

Cl

NO2

O

N H

O

Cl

O

O

H

Ts

H

H

H O

O

B

O O

MeO

B

O

O

B[(–)-Ipc]2

B[(+)-Ipc]2

OMe

O

OEt

OEt

O

NHBn

NHBn

B[(+)-Ipc]2

[(+)-Ipc]2B

MeO2C

MeO2C

O B

O

Ether, –78° a

THF, –78° a

THF, –78° a

Neat, rt, 14 d

Neat, rt, 14 d

Toluene, –78°, 18 h

NO2

Ts

Ts

OH

I

(30), 20

OH

NO2

(84), 82

(80), 84

CO2Me

(87), 92

(47), >95, 94:6 d.r.

OH

N H

OH

N H

OH

I (90), 20

Cl

Cl

OH

176, 705

719

719

58

58

290

364

C7

MeO

MeO

O

O

R

H

H

OMe

O

O

H

H

OTBDMS

O

O

Carbonyl Substrate

MeO2C

MeO2C

MeO2C

B

O

B

O

B

O

O

H

O

O

B[(–)-Ipc]2

B[(+)-Ipc]2

[(+)-Ipc]2B

B[(+)-Ipc]2

Allylborane Reagent

a

Neat, rt, 14 d

Neat, rt, 14 d

Neat, rt, 14 d

THF, –78°

THF, –78°

a

Ether, –78°

a

Conditions

I (95), 6

MeO

MeO

O

O

R

OMe

I

OH

OH

OTBDMS

OH

OTBDMS

(92)

(98)

CO2Me

CO2Me

(74), 80

(79), 80

95:5

(55), >95

OH

95:5

(51), >95

O2N

d.r.

OH

MeO

R

OH

R

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

58

57

57

719

719

176, 705

Refs.

365

O H

Br

Br

N3

Ts

B

O O Ph

B

O

B

N

B

O

Ph

O

O

Ts

N

O

Ph

O B O

O

OCH(Pr-i)2

OCH(Pr-i)2

Ph

B(2-d-Icr)2

OPh

MeO2C

a

–78°, 1 h

4 Å MS, toluene,

CH2Cl2, –78°

Ether, 0°, 1 h

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

THF, –78°

rt, 7 d OMe

I

OH

OH

OH

OH

I (98), 88

MeO

MeO

Br

N3

(91), 80 (80), 82 (89), 71

ether THF CH2Cl2 pentane

(75), 94

(64)

(63), 92

(81), 71

(88), 82 (100), 76

toluene

Solvent

CO2Me

OPh

OH

712

50

701

28

704

703

366

C7 O H

Carbonyl Substrate

B

O O

EtO

Cl

O

O

Ts

O

O

Ph

O

B

OEt

O

Ph

Ts

N

EtO

B

B

N

O

O

3,5-(CF3)2C6H3O2S

B N

O

OEt

Ph

Ph

OCH(Pr-i)2

OCH(Pr-i)2

3,5-(CF3)2C6H3O2S Cl N

Br

O

Allylborane Reagent

,

O

OEt

OEt

2

14 h

(5 mol%), THF, 80°,

(Ph3P)2Pt(CH2CH2)

O

2. H2O2

1.

O B

O

CH2Cl2, –78°

—

–78°, 1 h

4 Å MS, toluene,

Conditions

OH

OH

OH

OH

OH

Cl

Cl

Br

(75)

(81), 99

(76), 88

(95), 85

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

186

50

351

712

Refs.

367

O

MOMO

R1

O H

O H

O H

PivO

Br

SiMe2

Ts

B(Pr-n)2

B(Pr-n)2

B(OPh)2

N

B

B[(–)-Ipc]2

R2

N

Ph

Ts Ph

Ph,

SnBu3,

Ph BBr3, CH2Cl2

Ts

Ts HN H N

OPiv

2. Aldehyde, –78°

1.

Ether, –70° to rt

THF, 0° to rt, 18 h

THF, –78°, 3 h

MOMO

HO

R1

(98), 10:1 d.r.

OH

OH (58)

(91)

Me

2-CF3

Br

(51), 34

Ph

OH

(69), 48

Me

4-CF3

(76), 51

R2

R1

SiMe2R2

4-CF3

OH

OPiv

720

706, 702

709

707

368

C7

Bu3Sn

Bu3Sn

OTIPS

OTIPS

O

O

O

O

H

H

Carbonyl Substrate

OTBDMS

OTBDMS

OBz

OBz

Ts

Ts

B

N

B

N

Ts

N

Ph

Ts

N

Ph

Allylborane Reagent

Ph

Ph Bu3Sn Ts Ph N Br B N Ph, Ts CH2Cl2, rt, 16 h

OBz

OTBDMS

Bu3Sn Ts Ph N Br B N Ph, Ts CH2Cl2, rt, 16 h

OBz

OTBDMS

2. Aldehyde, –78°, 3 h

1.

2. Aldehyde, –78°, 3 h

1.

Conditions

,

,

SnBu3 OTIPS

SnBu3 OTIPS

OH

OBz

OH

OBz (65), 15:1 d.r.

O

(75), 17:1 d.r.

O

OTBDMS

OTBDMS

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

708

710

Refs.

369

C8

Ph

O

OTIPS

C6H13-n

O

MeO

O

n-C5H11

Bu3Sn

O

O

H

O

H

H

Br

OBz

Ts

B(Pr-n)2

B(Pr-n)2

B[(+)-Ipc]2

B(OPh)2

Ph

O B O

OTBDMS B

N

Ts

N

Ph Ph Bu3Sn Ts Ph N Br B N Ph, Ts CH2Cl2, rt, 16 h

OBz

OTBDMS

Ether, –70° to rt

Ether, –78° to rt, 4 h

THF, 0° to rt, 18 h

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

2. Aldehyde, –78°, 3 h

1.

,

HO

Ph

MeO

n-C6H13

n-C5H11

OH

OBz

Ph

OH

(95)

OH

OH

OTBDMS

(38)

(85), 95.4

(95), 97

(72), 17:1 d.r.

OH Br

SnBu3 OTIPS

O

702

722

709

28

708, 721

370

C9

C8

Ph

Ph

O

N

O

O

H

H

O

N

O H

Carbonyl Substrate

R

Br

S

Ts

Ts

Ts B

Ph

N

Ph

Ts

N

O B O

B

N

B(OPh)2

OBz

OTBDPS

S

OPiv N

Ph

Ts

N

Ts

N

Ph

B

Ph

Ph Ph

Allylborane Reagent

CH2Cl2, –78°, 2-3 h

CH2Cl2, –78°, 12 h

Sc(OTf)3 (10 mol%),

Toluene, –78°

THF, 0° to rt, 18 h

CH2Cl2, –78°, 2-3 h

Conditions

Ph

Ph

Ph

Ph

O N

R

Br

Br

Cl

R

(76), 97

OBz

OPiv S S

OTBDPS

(79), 87

(84), 92

(95), 10.5:1

(95)

OH

(94), 1:1 d.r.

OH

OH

OH

OH

O

N

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

710, 708

27, 28

50

709

710

Refs.

371

C10

R

Ph

R

OH

OH

O

O

O

O

H

H

H

Br

Br

Ts

O

O

O

B(OH)2

B

O

B

O

O

N B

B(OH)2

[(–)-Ipc]2B

OBz

OTBDPS

Ph

O

OCH(Pr-i)2

OCH(Pr-i)2

O

OCH(Pr-i)2

OCH(Pr-i)2

B[(–)-Ipc]2

Ts

N

Ph

—

–78°, 1 h

4 Å MS, toluene,

–78°, 1 h

4 Å MS, toluene,

—

Ether, –78° a

CH2Cl2, –78°, 2-3 h

R

Ph

Ph

R

Ph

OH

OH

OH

OH

OH

OH

OH

Br

Br

(90)

Cy

Ph

R (75)

(60)

(98), 89

95:5

80:20

d.r.

59:41

58:42

d.r.

OTBDPS

(83)

(98), 85

Cy

Ph

R

(57), 46:6:1 d.r.

OH

OBz (96), >20:1 d.r.

OH

714

712

712

714

176, 705

710, 708

372

C10

PMBO

Ph

OH

O

O

H

O

Carbonyl Substrate

H

R

R

S

S

S

S

B

Ts OTBDPS N

R=

R=

B

N

B

N

Ts

Ph

Ts

Ts

N

B(OH)2

Ph

Ts

N

Ph

Ts

N

Ph

Ph

Ph

Allylborane Reagent

N B

Ph

SnBu3,

Ts N B

Ph

SnBu3,

N B

Br

Ph, N Ts CH2Cl2, –78°, 2 h

Ts

Ph

SnBu3,

OTBDPS

Br

Ph, N Ts CH2Cl2, –78°, 2 h

R

Ph, N Ts CH2Cl2, –78°, 2 h

Ts Br

R

—

Conditions

PMBO

PMBO

PMBO

Ph

OH

R

O

(93), 7:1 d.r.

TBDPSO

O

(78), 2.5:1 d.r.

R

O

(100), 91:9 d.r.

OH

OH

OH

OH

(81), 55:45 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

708

708

723, 708

714

Refs.

373 OTBDMS

Ph

Ts

N

B

N

Ph

Ts

N

Ph

Ts

N

Ts

OTBDMS

B

Ts OTBDPS N

B

Ts OTBDPS N

B

Ts OTBDPS N

Ph

Ts

N

Ph

Ph

Ph

Ph

N B

N B

N B

OTBDMS

SnBu3,

OTBDMS Ph Ts N Ph, B N Br Ts CH2Cl2, –78°, 1.5 h

Br

Ph, N Ts CH2Cl2, –78°, 2 h

Ts

Ph

SnBu3,

OTBDPS

Br

Ph, N Ts CH2Cl2, –78°, 2 h

Ts

Ph

SnBu3,

OTBDPS

Br

Ph, N Ts CH2Cl2, –78°, 2 h

Ts

Ph

SnBu3,

OTBDPS

TBDPSO

O

(96), 8.5:1 d.r.

O

(97), 2:1 d.r.

TBDPSO

O

(98), 2:1 d.r.

TBDPSO

O

(100), 10:1 d.r.

TBDMSO

PMBO

PMBO

PMBO

PMBO

OTBDMS

OH

OH

OH

OH

191

708

708

708

374

C11

C10

N

Ph

OPMB

O

H

OH

N

OTBDPS O

O H

OSEM

O

O

N

O H

O H

Carbonyl Substrate

S

OBz

TBDMSO

OPiv

B

N

Ts

Ts

OPiv

B(OH)2

TBDMSO

S

PhO2S Ph

B

N

B

N

Ts

N

Ph

Ts

N

Ph

SO2Ph

N

Ph

Allylborane Reagent

Ph CH2Cl2, –78°, 2-3 h

Ph CH2Cl2, –78°, 2-3 h

—

CH2Cl2, –78°

Conditions

N

N

Ph

OPMB

O

OPMB

O

H

H

OH

N

OTBDPS O

S

OH

H

OH

(88), 4:1 d.r.

O

OSEM

BzO

OTBDMS

PivO

OTBDMS

(60), 80:20 d.r.

(99), 11.4:1 d.r.

H

OSEM

O

OPiv

OH

(95), 10.5:1 d.r.

OH

S

O

N

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

710

710

714

724

Refs.

375

C22

C13

OPMB

O

OPMB

O

H

AcO

MeO

TBDMSO

N

N H

H

O

H

O

O

H

H

H

OAc

MOMO

OTIPS

O

OTBDPS

O

O

H

H

OTMS

O

AcO

Ts B

N

Ph

B

N

Ph

Ts

B

N

B[(–)-Ipc]2

Ts

N

OPiv

TBDMSO

OPiv

TBDMSO

PhO2S Ph CH2Cl2, –78°, 2-3 h

Ts

N

Ph

THF, –78°, 1 h

1.5 h

Toluene, –78° to rt,

Ph —

SO2Ph

N

Ph

OPMB

O

OPMB

O

H

AcO

MeO

TBDMSO

N

N H

OH

MOMO

OH

H

H

H

OAc O

HO

OTMS

OAc

OH

PivO

OTBDMS

PivO

OTBDMS

(69), 1.7:1 d.r.

(92), 17:1 d.r.

(—)

O

OTIPS

(96), 11.8:1 d.r.

O

OTBDPS

726, 727

725

280

715, 716

376

C26

a

H

H

O

The reaction mixture was free of Mg2+ ions.

AcO

H

Carbonyl Substrate

B(Pr-n)2

Allylborane Reagent

THF, –70° to 0°, 30 min

Conditions

AcO H

(64)

H HO

Product(s) and Yield(s) (%), % ee

TABLE 5. ADDITION OF β-SUBSTITUTED REAGENTS (Continued)

728

Refs.

377

C2

C1

O

O

O

H

O

Carbonyl Substrate

Ph2N

OMEM

OPMP

OMe

OMe

O

"

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B

OPr-i

Allylborane Reagent

THF, –78° to 0°, 3 h

THF, –78°, 3 h

THF, –78°, 10 h

THF, –100°, 10 h

THF, –78°, 3 h

THF, –78°, 3 h

Toluene, 80°, 12 h

Conditions

+ H

OH

(27)

(—), 93, >99:1 d.r.

(—), 95, >99:1 d.r.

(59), 92, >99:1 d.r.

Ph2N (40), >95, >95:5 d.r.

OH

I (75), >95

I OMEM

OH

NPh2

(68), >98, >20:1 d.r.

(57), 90, >99:1 d.r.

OH

Product(s) and Yield(s) (%), % ee

OPMP

OH

OMe

OH

OMe

OH

OH

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS

730, 731

505

388

407

48, 503

48

729

Refs.

378

C2

O

H

Carbonyl Substrate

O

B

O

PhMe2Si

Ph

Ph2N

BR2

2. H2O2, NaOH

4h

1. Ether, –78° to 0°,

THF, –78° to rt, 4 h

–70° to 0°

THF, –78° to 0°, 3 h

Conditions

THF, –78°, 12 h

B[(+)-Ipc]2 THF, –78°, 4 h

B[(–)-Ipc]2

B[(+)-Ipc]2

BEt2

BEt2

B[(+)-Ipc]2

Allylborane Reagent

+

Ph

OH

PhMe2Si

OH

OH

OH

OH

HO

HO

(73), 91

(—)

(75), 92, >97:3 d.r.

(75), 84

(–)-Ipc

(28)

(82), —

H

OH

Cy

R

(61)

(41), >95, >95:5 d.r.

Ph2N

OH

>99:1

>99:1

d.r.

NPh2

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

138, 136a

734

157

733

732

730, 731

Refs.

379 O

B

O

B

O

B

O

B

O

B

O

O

O

O

O

O

TMS

OMe

OMOM

OMe

OTHP

OTHP

TMS

BBN

Neat, rt, 2 d

Neat, rt, 2 d

Neat, rt, 7 d

—

Neat, rt, 48 h

THF, –78°, 3 h

(50)

H2SO4

I OTHP

O

OH

2:98

98:2

II I:II

(86), 88:12 d.r.

(89), 92:8 d.r.

(85), 93:7 d.r.

OMe

OMOM

OH

OMe

OH

H

(70-80), 78:22 d.r.

(61)

KOH

OH

I + II

+ I Work-Up

TMS

I (70-80), 78:22 d.r.

H TMS

47, 36

47, 36

36

47, 33,

104

34a

735, 736

380

C2

O

H

Carbonyl Substrate

B

O

B

O

"

B

O

O

O

O

TMS

O

SEt 0.65 equiv 30:70 E:Z

SMe 8:92 E:Z

Ph

MeO

O

B

O

B

O O

Allylborane Reagent

O B O

,

—

—

50°, 3 h; rt, 16 h

Br, Ph Cl2Pd(PPh3)2, THF,

IZn

THF, rt, 16 h

rt, 36 h

Petroleum ether,

Neat, rt, 2 d

Conditions

Ph

OH

OH

SEt

SMe

(91), 93:7 d.r.

(80), 9:1 d.r.

(86), 92:8 d.r.

(57), >99:1 d.r.

(76), 95:5 d.r.

TMS

I (57), >99:1 d.r.

I

OH

OMe

OH

O

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

737

737

79

79

47, 36

47

Refs.

381

Si

Ph

Cl

PhMe2Si

CyO

Me

TMS

Me

O B

"

O

O

O

B

O

B

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OCH(Pr-i)2

OCH(Pr-i)2

B

O

B

O

O

50°, 3 h

–100°

Toluene/pentane (10:3),

2. Aldehyde, rt, 16 h

O B

, O I, Cl2Pd(PPh3)2, THF,

1. IZn Ph

THF, rt, 16 h

–78°, 3-4 h

4 Å MS, toluene,

–78°, 3-4 h

4 Å MS, toluene,

Petroleum ether

SiMe2Ph

(70), 75

(61), >99:1 d.r.

(95), 84, >99:1 d.r.

Cl

I (61), >99:1 d.r.

OH

(94), 69, >99:1 d.r.

(92), 94:6 d.r.

SiMe2(OCy)

TMS

I Ph

OH

OH

OH

OH

738

79

79

39, 40

38, 40

47

382

C2

O

H

Carbonyl Substrate

n-Bu

n-Bu

Bu-n

n-Bu

MeO

OMe

B

O

B

O

B

O

B

O

O

B

O

B

O

O

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Allylborane Reagent

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

Neat, rt, 5-8 d

Neat, rt, 5-8 d

6d

Petroleum ether, 20°,

3d

Petroleum ether, 20°,

Conditions

n-Bu

OH

OH

OH

OH

OH

MeO

OH

Bu-n

Bu-n

Bu-n

OMe

(86), 67, 96:4 d.r.

(88), 72, 96:4 d.r.

(83), 88:12 d.r.

(83), 95:5 d.r.

(61), 95:5 d.r.

(50), 70:30 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

740

740

55

55

739

739

Refs.

383

RO

CF3

H

O H

R = Bn

TBDMSO TBDMSO

R=

O

OTBDMS

OTBDMS O

Ph

Ph

Ph

O

O

Ph

B

O

OMOM

MEMO

O

O

O

B

O

O

OCH(Pr-i)2

OCH(Pr-i)2

O

OCH(Pr-i)2

OCH(Pr-i)2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B

O

B

O

O

–78°, 2 h

rt, 24 h

Ether, –78°, 2 h;

THF, –85°, 18 h

–100°

Pentane/ether (1:1),

–78°, 72 h

4 Å MS, toluene,

–78°, 72 h

4 Å MS, toluene,

RO

RO

RO

CF3

OH

Ph Ph

O

OH

B

Ph

O Ph

(—)

(40), 93, >20:1 d.r.

OH

(65)

OR

(75), 96, >19:1 d.r.

(82), 60

(75), 61

OMOM

OH

OMEM

OH

OH

OH

670

175

742

249

741

741

384

C2

RO

R = Bn

H R = Bn, TBDPS

O

Carbonyl Substrate

EtO2C

PhMe2Si

PhMe2Si

O

B

O

B

O

B

O

O

O

O

O

O

B(OPr-i)2

O

OCH(Pr-i)2

O

OCH(Pr-i)2

OCH(Pr-i)2

O

THF, –78°, 4 h

Conditions

rt, 24 h

Sc(OTf)3, toluene,

–78°, 72 h

4 Å MS, toluene,

–78°, 72 h

4 Å MS, toluene,

CH2Cl2, rt, 3 d

OPr-i 4 Å MS, toluene, –78° O

OPr-i

OCH(Pr-i)2

B

O

B[(+)-Ipc]2

Allylborane Reagent

RO

RO

RO

RO

RO

RO

O

OH

OH

OH

PhMe2Si

OH

PhMe2Si

OH

O

(70), 90

(85), 88

(33), >20:1 d.r.

(29), 48

(36), 50

(59)

(99)

TBDPS

Bn

R

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

26

741

741

741, 744

743

734

Refs.

385

C3

O

n-BuO

H

O

O

R= PMB

H

OMe

OMe

PhMe2Si

Et

EtO2C

O O 2

B[(+)-Ipc]2

O

OEt

OEt

O

B[(–)-Ipc]2

B[(+)-Ipc]2

B

O

B

O

O ,

O

benzene, rt

2

OEt

OEt

Pt(dba)2, PCy3,

O B ,

THF, –78°, 3 h

THF, –78°, 3 h

THF, –78°, 4 h

3. NaOH, H2O2

2. Aldehyde, –78°, 3 h

1.

O

rt, 24 h

Sc(OTf)3, toluene,

O

OMe

OH

OMe

OH

(68), 90, >99:1 d.r.

(65), 88, >99:1 d.r.

(85), 95

(58), 66, >19:1 d.r.

(53), 19:1 d.r.

SiMe2Ph

Et

O

OH

OH

OH

n-BuO

RO

RO

O

48

48

734

185

26

386

C3

O

O

H

H

Carbonyl Substrate

OMe

OMe

Ph2N

Ph2N

O

B

O

OMOM

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

"

B[(+)-Ipc]2

Allylborane Reagent

THF, –78°, 3 h

THF, –78°, 3 h

THF, –78°, 12 h

THF, –78° to 0°, 3 h

THF, –78° to 0°, 3 h

2. H2O2, NaOH

4h

1. Ether, –78° to 0°,

—

THF, –78°, 3 h

Conditions

OMe

OH

OMe

OH

OH

Ph2N

OH

Ph2N

OH

OH

OH

I (66), >95

I OMOM

OH

(68), 90, >99:1 d.r.

(65), 88, >99:1 d.r.

(70), 95

(47), >95, >95:5 d.r.

(45), >95, >95:5 d.r.

(63), >97:3 d.r.

(62), 90, >99:1 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

48

48

138, 136a

730, 731

730, 731

157

745

48, 156

Refs.

387

B

Ph

N

OMOM

OMe

Ph

O

O

OSEM

B

O

B

O

O

O

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

N

,

Neat, 60°, 6 h

Neat, 20°, 2 d

Ether, pentane, –100°

–78°, 3 h

2. Aldehyde, THF,

MeOB[(–)-Ipc]2

Ph LDA,

1. Ph

2. H2O2, NaOH

4h

1. Ether, –78° to 0°,

THF, –100° to rt

Ph

Ph

OMOM

OH

OMe

OH

OH

N

OH

OH

OH

OSEM

OH

(88), 89:11 d.r.

(94), 92:8 d.r.

(81), 97

(48), >95:1 d.r.

(67), 90, >97:3 d.r.

(70), >95

47, 36

36

47, 33,

505

746

157

189

388

C3

O H

Carbonyl Substrate

SR

MeO

OTHP

OTHP

O

O

O

O

(90) (94) (95)

Et Et Et

1.0 1.0 0.4

44:56 73:27 44:56

91:9

27:73

56:44

d.r. 91:9

(91)

SR

(68), 95:5 d.r.

Me

OH

OMe

R

—

rt, 36 h

OH

I (70-80), 80:20 d.r.

(70-80), >80:20 d.r.

1.0

O

Petroleum ether,

(94), 93:7 d.r.

(88), 80:20 d.r.

TMS

OMe

Equiv

B

O

—

I OTHP

OH

O

OH

O

OH

Product(s) and Yield(s) (%), % ee

E:Z

O

O

O

Neat, rt, 48 h

Neat, 20°, 4 d

Neat, rt

Conditions

8:92

B

O

B

O

B

O

TMS

B

O

OMe

B

O

Allylborane Reagent

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

737

47, 33

104

34a

47

47, 36

Refs.

389 Bu-n

n-Bu

MeO

TMS

Et

B

O O

B

O

B

O

B

O

O

O

O

B(OMe)2

B(OMe)2

B(OMe)2

Neat, rt, 5-8 d

Neat, rt, 5-8 d

20°, 9 d

Petroleum ether,

rt, 3 d

Petroleum ether,

Ether, –75°

Ether, –75°

Ether, –75°

n-Bu

OH

OH

OH

OH

OH

OH

OH

Bu-n

OMe

TMS

Et

(82), 90:10 d.r.

(70), 95:5 d.r.

(74), 98:2 d.r.

(70), 94:6 d.r.

(36)

(44), 90:10 d.r.

(31)

55

55

739

47

43

43

43

390

C3

O H

H

Co2(CO)6

O

O

Carbonyl Substrate

MeO

OMe

"

B[(–)-Ipc]2

B[(–)-Ipc]2

BBN

BEt2

BEt2

B(OMe)2

B(OPr-i)2

Allylborane Reagent

, HBBN, pentane, rt, 24 h

THF, –78° to rt, 15 h

THF, –78° to rt, 15 h

2. Ketone, rt, 2 h

1.

Pentane, rt, 2 h

–70° to 0°

Ether, –75°

rt

Conditions

OH

(CO)6Co2

(CO)6Co2

I (80)

I

HO

HO

OH

OH

(80)

OMe

OH

OMe

OH

(93)

1h

3h

Time (82)

(84)

>97.5:2.5 d.r.

(20), >95,

94:6 d.r.

(76), >96,

(34), 98:2 d.r.

neat

toluene

Solvent

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

747

747

103

103

732

43

744

Refs.

391

RO

H

R = Bn

R = PMB

R = TBDMS

R = Bn, PMB

R = TBDMS

R = PMB

R = Ac

O

OMe

PhMe2Si

Cl

OMOM

OMe

B

O O

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc] 2

B[(–)-Ipc]2

B[(+)-Ipc]2

B(OBu-n) 2

benzene, –100° to rt

THF, cyclohexane,

Ether, pentane, –100°

12 h

Ether, –78° to rt,

—

THF, –78°, 4 h

Ether, –78°

–78° to 0°

OMe FB(OBu-n)2

–

RO

OH

Cl

OH

OMOM

OH

OMe

I

OMe

OH

OH

OH

PhMe2Si

I (82), 95

RO

RO

RO

RO

RO

RO

OH

(72), 95

PMB

(46), 88

(49), 95

(—), 99

(74), 90

Bn

R

(85), >95, >95:5 d.r.

(80), 90

(59)

545

505

749

749

734

631

748

46

392

C3

R = Bn

R = Ac

TBDPSO

RO

O H

O H

Carbonyl Substrate

EtO2C

Bu-n

Bu-n

n-Bu

n-Bu

THPO

B

O

B

O

B

O

O

O

O

O

O

B

O

B

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

B

O

Allylborane Reagent

Neat, rt, >12 d

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

—

Conditions

TBDPSO

RO

RO

RO

RO

RO

I

OH

OH

OH

OH

OH

O

Bu-n

Bu-n

Bu-n

Bu-n

O

OTHP

(75)

(46), 80, 97:3 d.r.

(56), 73, 97:3 d.r.

(57), 82, 97:3 d.r.

(56), 85, 97:3 d.r.

(71), 13:1 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

59

740

740

740

740

52

Refs.

393

O B O

R1 = see table

"

R1 = (–)-8-phenylmenthyl

R1O2C

rt

(51), 80 (95), 82 (86), 75 (74), 56 (24), 66 (6), 62

Ph 2-Nph 2-Nph 4-MeOC6H4 4-PhC6H4 3,5-Me2C6H3

" " " " " "

26 d

8d

36 d 14 d 14 d 14 d 14 d 14 d

toluene

neat

toluene toluene CH2Cl2 toluene toluene toluene

R

2

Ph

(70), 10

(78), 7

—

H

(64), –6

—

14 d

(89), 22

—

neat

O

8d

neat

(92), 0

Et

>12 d

neat O

R2 —

R1

Time

I

I (80), 82

Solvent

2. pTSA

1. Neat, rt, 14 d

59, 26

59

394

C3

O

OBn

PhS

H

O H

Carbonyl Substrate

TMS

TMS

MeO

O

OMe

THPO

O

O

O

TMS

B

O

B

O

B

O

B

O

O

O

B

O O

B

O O

Allylborane Reagent

O B O

Neat, rt, 4 d

22°, 4 d

Petroleum ether,

22°, 7 d

Petroleum ether,

22°, 7 d

Petroleum ether,

—

Cl

THPO

Li,

Conditions

OH

OBn TMS

OH

OBn O

OH

OBn OMe

OH

OBn O

OH

OBn OMe

PhS

OH

(52), 58:42 d.r.

TMS

(94), 92, 60:40 d.r.

(97), 92, 57:43 d.r.

TMS

(87), 92, 82:18 d.r.

(—), 88:12 d.r.

OTHP

(50), 13:1 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

521

275

275

275

275, 750

52

Refs.

395

H

H

NBn2

O H

R = TBDMS

R = TBDMS, Bn, THP

OR

O

OBz

O

TMS

Cy

MeO

CyO

Me

CyO

Me

Si

Si

Me

Me

O

B

O O

BBrCy

B

O

B

O

B

O

O

O

O

O

O

–78° to 0°, 1 h

HBCy2, n-Bu4NBr,

Br ,

Neat, rt, 4 d

1h

2. Aldehyde, 0° to rt,

1.

6-8 kbar

OPr-i 4 Å MS, toluene, –78°, 3-4 h

OPr-i

O

OPr-i 4 Å MS, toluene, –78°, 3-4 h

OPr-i

OMe

III

Cy

II I+II

OMe

+

III

(71), >95:5 d.r.

(8)

(46)

(15) (82)

(83), 50:50 d.r.

THP

Bn

TBDMS (24) (57)

R

RO

OMe

+

OH

(90), 23:1 d.r. SiMe2(OCy)

OH

OH

(80), 84:16 d.r. SiMe2(OCy)

NBn2 TMS

OR

I

OH

RO

RO

OH

OBz

OH

OBz

OH

521

751, 680

739

38, 40

38, 40

396

C3

O

O

N

N

Boc

O

Boc

O

H

H

Carbonyl Substrate

N Ph

B[(–)-Ipc]2

B[(+)-Ipc]2

TMS

Ph

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

TMS

Cl

Cl

Cl

BBN

(i-Pr)2NMe2Si

(i-Pr)2NMe2Si

Allylborane Reagent

THF, –78°

2. KF, H2O2

1. KHCO3

2. KF, H2O2

1. KHCO3

6h

Ether, THF, –95°,

6h

Ether, THF, –95°,

6h

Ether, THF, –95°,

2. KF, H2O2

1. Ether, –78°, 3.5 h

2. KF, H2O2

1. Ether, –78°, 3.5 h

Conditions

N Boc

OH

N Boc

Cl

N Boc

O

I

N Boc

N

OH

I

I

I

Ph

OH

I (45), 67:33 d.r.

O

OH

I (72), >97:3 d.r.

I (37), 62:38 d.r.

O

OH

I (45), 2:1 d.r.

O

OH

Ph

(58), 1.2:1 d.r.

(57), >98:2 d.r.

(68), 95:5 d.r.

(57), >95:5 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

160

278

278

753, 754

753

753, 754

511

752, 45,

752

Refs.

397

O O

TBDMSO

O H

OBn

O H

"

B[(+)-Ipc] 2

B[(–)-Ipc]2

B[(–)-Ipc]2

B(OMe) 2

SiMe2Bn

SiMe2Ph

Ph

N

OMOM

n-Pr

n-Pr

Ph

"

N

N

2d

THF, hexane, rt,

THF, –78° to rt

THF, –78° to rt

THF, –78°

–78°, 3 h

2. Aldehyde, THF,

MeOB[(+)-Ipc]2,

Ph LDA,

1. Ph

–78°, 3 h

2. Aldehyde, THF,

MeOB[(–)-Ipc]2,

Ph LDA,

1. Ph

,

,

O OMOM

OH

(52), 1.8:1 d.r.

BnO n-Pr SiMe2Bn

OH

(56), 1.8:1 d.r.

BnO n-Pr SiMe2Ph

OH

(75-85), >20:1 d.r.

O

TBDMSO

TBDMSO

I (40), >95:5 d.r.

I (40), >95:5 d.r.

I (48), 1.2:1 d.r.

755

206

206

160

746

746

398

C3

O

O

O H

Carbonyl Substrate

Ph

Ph

Cl

Cl

Ph

Ph

N

N

"

"

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

N

N

THF, –78°

–78°, 3 h

2. Aldehyde, THF,

MeOB[(+)-Ipc]2,

Ph LDA,

1. Ph

THF, –78°

–78°, 3 h

2. Aldehyde, THF,

MeOB[(–)-Ipc]2,

Ph LDA,

1. Ph

Ether, –95°, 4 h

Ether, –95°, 4 h

,

,

Conditions

O

O

O

I

N

OH

Cl

OH

Cl

I (41), 2.7:1 d.r.

I (41), 2.7:1 d.r.

I (43), >95:5 d.r.

O

O

O

OH

Ph

Ph

(43), >95:5 d.r.

(68), 61:39 d.r.

(65), 99.5:0.5 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

160

746

160

746

756

756

Refs.

399 RMe2Si

PhMe2Si

PhMe2Si

TBDPSO

B

O

B

O

B

O

O

O

O

O

O

B

O

O

B[(+)-Ipc]2

CH2Cl2, rt, 12-24 h

O

OPr-i –78°

4 Å MS, toluene,

OPr-i 4 Å MS, toluene, –78° O

OPr-i

OPr-i 4 Å MS, toluene, –78° O

OPr-i

OPr-i

O

–78°, 1 h

BF3•Et2O, THF,

O

O

O

O

O

(79) (82)

menthofuryl CyO

>95:5

>96:4

d.r. 95:5

(96), 20:1 d.r.

(90), 23:1 d.r.

(93)

SiMe2R

SiMe2Ph

SiMe2Ph

OTBDPS

(55), 10:1 d.r.

2-(5-methyl)furyl

OH

OH

OH

OH

(73)

R

O

O

O

O

O

OH

40

158, 38,

39, 40

39, 40

61

533

400

C3

O

O

O H

Carbonyl Substrate

B

O

B

B

"

B(OPr-i)2

R = menthofuryl

RMe2Si

O

R = menthofuryl

RMe2Si

RMe2Si

O

O

O

O

O

O

O

–78°

4 Å MS, toluene,

–78°

4 Å MS, toluene,

Conditions

Toluene, rt, 3 h

CH2Cl2, 12 h

OPr-i 4 Å MS, toluene, –78° O

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Allylborane Reagent

O

O

I

OH

OH

SiMe2R

SiMe2R

0°

rt

Temp (—)

(93)

(85), 92:8 d.r.

d.r. 92:8

87:13

(79), >96:4 d.r.

(88)

CyO

O

92:8 85:15

(85)

menthofuryl

OH

94:6

2-(5-methyl)furyl (90)

d.r.

SiMe2R

R

O

I (90), 89:11 d.r.

O

O

O

O

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

741

741, 744

757

757

40

158, 38,

Refs.

401

O

O

O H

Ph2N

Ph2N

Cy

O B O

O

2

B[(+)-Ipc]2

B[(–)-Ipc]2

BBrCy

O

OEt

OEt

–78° to 0°, 1 h

HBCy2, n-Bu4NBr,

Br ,

THF, –78° to 0°, 3 h

THF, –78° to 0°, 3 h

1h

2. Aldehyde, 0° to rt,

1.

2. NaOH, H2O2

1. –78°, 3 h

O

O

O

O

OH

OH

O

+

O

O Ph2N

+

O

O

Cy

OH

OH

O Ph2N

O

O

OH

H

OH

H

OH (19)

NPh2

(26)

(28), >95, >95:5 d.r.

NPh2

(23), >95, 23:6 d.r.

(40), 85:15 d.r.

(71), >19:1 d.r.

730, 731

730, 731

751, 680

185

402

C4

C3

O

EtO

O

O

O

O

O

O

O

H

O

H

H

Carbonyl Substrate

OSEM

OTHP

O

O

B

O

O

O

O

2

B[(–)-Ipc]2

B[(+)-Ipc]2

O

OPr-i

OPr-i

O

OEt

OEt

B[(+)-Ipc]2

B

O

B

O

Allylborane Reagent

THF, –78°

THF, –78°

THF, –78°

6 kbar, 45°, 80 h

Petroleum ether,

–78°

4 Å MS, toluene,

2. NaOH, H2O2

1. –78°, 3 h

Conditions

O

EtO

O

O

HO

O

OTHP

OH

OH

OSEM

OH

O

OH

OH

OH

(83), 96

(85), 96

(65-68), 82

(85), 14:1 d.r.

(79), >99:1 d.r.

(66), 1:1 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

138, 140

138, 140

759

104

194, 758

185

Refs.

403 O

H

H

Co2(CO)6

O

R

Cy

Et O

BBN

BBN

B[(–)-Ipc]2

BBrCy

B

O

TMS

TMS

EtO2C

TMS

n-Bu

–78° to 0°, 1 h

HBCy2, n-Bu4NBr,

Br ,

15 h

THF, –78° to rt,

1h

2. Aldehyde, 0° to rt,

1.

rt, 16-24 h

Sc(OTf)3, toluene,

2. KOH

1. THF, –78°, 3 h

2. NaOH

1. THF, –78°, 3 h

H

+

TMS H

II

(61), 1:1 d.r.

>97.5:2.5 >97.5:2.5

(73), >96 (65), >96 OMOM

d.r.

(84), >98:2 d.r.

R

OH

Et

O

TMS

n-Bu

OMe

R

+

I + II (59), I:II = 98:2

Cy

(CO)6Co2

n-Bu

II I + II (53), I:II = 93:7

O

I

I

OH

H

H

747

751, 680

26

735

736

404

C4

n-Pr

H

O H

O H

Co2(CO)6

O

Carbonyl Substrate

Cl

Cl

OTHP

PhMe2Si

MeO

B

O

B

O

B

O

O

O

O

O

O

O

OCH(Pr-i)2

OCH(Pr-i)2

O

OCH(Pr-i)2

OCH(Pr-i)2

B[(+)-Ipc]2

B(Pr-n)2

B[(–)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

(10:3), –100°

Toluene/pentane

(10:3), –100°

Toluene/pentane

Neat, rt, 48 h

Ether, –78°, 12 h

Neat, 60°

THF, –78°

THF, –78° to rt, 15 h

Conditions

n-Pr

n-Pr

n-Pr

n-Pr

n-Pr

OMe

OH

OH

OH

Cl

(77), 98

Cl

(82), 93

(85), 96

(70-80), >80:20 d.r.

(79), 92

(62)

SiMe2Ph

OTHP

OH

OH

OH

OH

(44), >95, >97.5:2.5 d.r.

(CO)6Co2

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

738

738

34a

138, 136a

238

760

747

Refs.

405

i-Pr

O H

OMe

OPh

Et

Ph

PhMe2Si

Bu-n

n-Bu O

B[(+)-Ipc]2

B(OBu-n)2

B–Et2SePh

O

O

O B

B

O

B

O

,

O O

O

,

FB(OBu-n)2

–

THF, –78°, 3 h

OPh

12 h

2. Et3B, –78° to rt,

–78°, 30 min

LDA, THF,

1. PhSe

80°, 5 h

I Pd2(dba)3, EtOAc,

Ph

PhMe2Si B

Neat, rt, 5-8 d

Neat, rt, 5-8 d

,

,

i-Pr

i-Pr

n-Pr

n-Pr

n-Pr

n-Pr

Et

Ph

OMe

OH

i-Pr II

OH

(57), 88, >99:1 d.r.

I + II (72), I:II = 3:1

+

(85), 75:25 d.r.

OPh

(70), >99:1 d.r.

(79), 90:10 d.r.

(76), 95:5 d.r.

SiMe2Ph

Bu-n

Bu-n

I OPh

OH

OH

OH

OH

OH

48

46

692

761

55

55

406

C4

i-Pr

O H

Carbonyl Substrate

O

Ph Ph

Ph

Cl

OMe

"

"

O

Ph

B

O

B

O

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

Cl, LDA, ether, –78°

MeOB[(–)-Ipc]2,

–78°, 12 h

Ether, pentane, –100°

Ether, –78°, 2 h

Ether, –78°, 2 h

rt, 24 h

Ether, –78°, 2 h;

3. Aldehyde

2. BF3•OEt2

1.

THF, –78°, 3 h

Conditions

I

OH

Ph

O

OH

O

OH

OH

B

B

Cl

OH

Ph

O

O

OMe

I (73), 89

i-Pr

Ph

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

OH

Ph

Pr-i

(34), 84, >20:1 d.r.

(85), 95

(—)

(—)

OH

(—), 77

(62), 88, >99:1 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

138, 136a

505

175

175

175

159, 762

48

Refs.

407 MeO

O

O

OTHP

O

B

O

B

O

O

O

O

O

O

B

TMS O

TMS

B

O

B

O

OMe

OMOM

OMe

B

O

B

O

O

O

rt, 36 h

Petroleum ether,

rt, 2 d

Petroleum ether,

Neat, 20°, 14 d

—

Neat, rt, 2 d

Neat, rt, 2 d

Neat, 20°, 2 d

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

OMe

OH

O

OH

O

OH

OTHP

OH

O

OH

(77), >98:2 d.r.

TMS

(86), >95:5 d.r.

TMS

(76), 89:11 d.r.

(70-80), 80:20 d.r

(57), 68:32 d.r.

(90), 80:20 d.r.

(94), 89:11 d.r.

OMe

OMOM

OH

OMe

OH

47, 33

47

47

104

47, 36

47, 36

36

47, 33,

408

C4

i-Pr

O H

Carbonyl Substrate

MeO

"

B

O

O

B

O

O B O

O

B(OPr-i)2

B

O

O

OCH(Pr-i)2

OCH(Pr-i)2

0.4

56:44

O

1.0

O

Equiv

Z:E

O

>95:5

Bu-n

n-Bu

SR

B

O

Allylborane Reagent

–78°, 72 h

4 Å MS, toluene,

Toluene, rt, 8 h

8 kbar, 46°, 5 h

Petroleum ether,

20°, >20 d

Petroleum ether,

Neat, 4 kbar, rt

Neat, 4 kbar, rt

—

Conditions

OH

OH

OH

i-Pr

i-Pr

OH

OH

(95)

Me Et

OMe I

Bu-n

(79), 88

(80)

(31), 98:2 d.r.

(87), 92:8 d.r.

(81), 99:1 d.r.

5:95

Z:E >95:5

(90)

R

Bu-n

SR

I (70), 97:3 d.r.

i-Pr

i-Pr

i-Pr

i-Pr

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

741

741, 744

739

739

55

55

737

Refs.

409

Cl

O H TMS

c-C5H9

Cy

Bu-n

EtO2C B O

O

O

O

B

O

O

OPr-i

OPr-i

O

OCH(Pr-i)2

OCH(Pr-i)2

O

BBr(C5H9-c)

BBrCy

O

B

O

B

O

O

–78° to 0°, 1 h

HBCy2, n-Bu4NBr,

Br ,

–78° to 0°, 1 h

n-Bu4NBr,

HB(C5H9-c)2,

Br ,

Neat, rt, 4 d

1h

2. Aldehyde, 0° to rt,

1.

1h

2. Aldehyde, 0° to rt,

1.

rt, 24 h

Sc(OTf)3, toluene,

–78°, 72 h

4 Å MS, toluene,

–78°, 72 h

4 Å MS, toluene,

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

OH

TMS

C5H9-c

OH

Cl

O

Cy

OH

n-Bu

O

OH

OH

(90), 65:35 d.r.

(60), >98:2 d.r.

(72), >98:2 d.r.

(32), >20:1 d.r.

(80), 81

(82), 88

521

751, 680

751, 680

26

741

741

410

C4

TBDMSO

TBDMSO

Et

O

O H

O H

Carbonyl Substrate

RMe2Si

OMOM

Cl

Cl

OMEM

TMS

B(OMe)2

B

O

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

TMS

O

O

BBN

O

OPr-i

OPr-i

Allylborane Reagent

–78°

4 Å MS, toluene,

THF, rt

Ether, –95°, 4 h

Ether, –95°, 4 h

—

THF, –78°, 3 h

Conditions

I

Et

OH

TBDMSO

TBDMSO

TBDMSO (58), 86:14 d.r.

(55), 95:5 d.r.

TMS

(67) (82) (76)

menthofuryl CyO

SiMe2R 2-(5-methyl)furyl

OH

>95:5

94:6

>96:4

d.r.

OMOM (40), 70:30 d.r.

OH

Cl

OH

Cl

OH

OMEM (69), 94, >99:1 d.r.

TBDMSO

R

+ II I + II (68), I:II = 55:45

TBDMSO

Et

TMS

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

40

158, 38,

602

651

651

388

735, 736

Refs.

411

RO

H

R = TBDMS

R = TES

R = PMB

O

O B

B

O

OMOM

OMOM

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

R = menthofuryl

RMe2Si

Cl

O B

R = menthofuryl

RMe2Si

RMe2Si

O

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Ether, –95°, 4 h

THF, –89°, 18 h

THF, –78° to rt

–78°

4 Å MS, toluene,

–78°

4 Å MS, toluene,

–78°

4 Å MS, toluene,

RO

RO

RO

TBDMSO SiMe2R

Cl

OH

OMOM

OH

OMOM

OH

64:36

(55), 85:15 d.r.

(60), >95:5 d.r.

(83), 8:1 d.r.

(80), 55:45 d.r.

OH

(82), 96:4 d.r.

SiMe2R

(70)

CyO

TBDMSO

(80)

menthofuryl

OH

67:33

(58)

2-(5-methyl)furyl 55:45

d.r.

SiMe2R R

TBDMSO

OH

651

764

763

757

757

40

158, 38,

412

C4 H

OH

O H

O H

R = TBDMS

R= TBDPS

R = PMB

R= TBDMS

TBDPSO

RO

O

Carbonyl Substrate

Cl

O

B

PhMe2Si

PhMe2Si

Cl

O OMe

B[(–)-Ipc]2

B

O

"

B

O

B[(+)-Ipc]2

B[(+)-Ipc]2

O

O

O

O

–100°

Ether, pentane,

Ether, –95°, 4 h

Conditions

OMe B O OMe, –78° to rt, 1.5 h

O

B(NMe2)2,

2. L.A., –78° to rt, 3 h

1.

Ether, –95°, 4 h

OPr-i 4 Å MS, toluene, –78° O

OPr-i

–78°

OPr-i 4 Å MS, toluene, –78° O 4 Å MS, toluene,

OPr-i

Allylborane Reagent

I SiMe2Ph

OH

OH

Cl

Solvent THF ether THF

FeCl3 Ti(OPr-i)4 ZrCl4

OH

Cl

OH

SiMe2Ph

L.A.

OH

TBDPSO

RO

OH

I (91), >20:1 d.r.

RO

RO

RO

OH

(72)

(84)

(61)

77:23

72:28

87:13

d.r.

(68), 93:7 d.r.

(92), 1.5:1 d.r.

(75)

(90), 96:4 d.r.

(56), 95:5 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

299

765

39, 40

39, 40

743

505

651

Refs.

413

MeO

BzO O

OMe O

O

H

H

PhO

Me

PhO

Me

Si

Si

Me

Me

PhMe2Si

PhMe2Si

O B O

O

O

O

O

O

O

O

B[(+)-Ipc]2

B

O

B

O

B

O

B

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

4 kbar, 3 d

Petroleum ether,

–100°

Ether, pentane,

–78°

4 Å MS, toluene,

–78°

4 Å MS, toluene,

OPr-i 4 Å MS, toluene, –78° O

OPr-i

OPr-i 4 Å MS, toluene, –78° O

OPr-i

OH

OH

OH

OH

(89), 8:1 d.r.

(82), 15:1 d.r.

I (93), 97.5:2.5 d.r.

(80), 13:1 d.r.

SiMe2(OPh)

(53), 2:1 d.r.

SiMe2(OPh)

SiMe2Ph

SiMe2Ph

OMe OH

O

O

O

I (82), 2:1 d.r.

MeO

BzO

BzO

BzO

BzO

O

53

505

38, 40

38, 40

40, 39

40, 39

414

C4

TBDPSO

O

O

O

PhthN

O

O

O

O

O

H

H

RO

OR

O

OH

O

H

Carbonyl Substrate

Ph Ph

Ph O

Ph

OMOM

OMEM

OMe

OMe

O

B

O

B[(–)-Ipc]2

B[(–)-Ipc]2

B

O

B(OMe)2

B[(+)-Ipc]2

Allylborane Reagent

CH2Cl2, –78°

THF, –78°

rt

THF, –95°, 3 h;

24-48 h

CH2Cl2, –78° to rt,

THF, –78°

Conditions

O

O

OH

OMe

OMOM

(83)

(—) (—)

t-Bu

Ph

RO

OR

Ph

O

OH

B

Ph

O Ph

(60), >96.5:3.5 d.r.

O

PMB

R

TBDPSO

O

OH

OMEM (87), 95, >99:1 d.r.

O

PhthN

HO

I (70-75), 95:5 d.r.

I

O

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

201

771

769, 770

768

118, 767,

766, 767

Refs.

415

C5

Et

O H

O

O

H

H

RO

Cl

n-Pr

B[(+)-Ipc]2

O

R = TBDMS

B O

O

B[(–)-Ipc]2

B[(+)-Ipc]2

O

OPr-i

OPr-i

B[(+)-Ipc]2

B[(–)-Ipc]2

SiMe2Ph

PhMe2Si

Cl , LiNCy2, ether, –78°

MeOB[(–)-Ipc]2,

–78°, 5 h

4 Å MS, toluene,

–78°, 12 h

–78°, 12 h

3. Aldehyde

2. BF3•OEt2

1.

THF

THF, –78°

Et

OTBDMS

OH

OH

OH

14 h

–50°

(84), 69

(83), 96

(85), 96

(78), 99, 99:1 d.r.

8:1 10:1

(67)

6h

–23°

Cl

3:1

(79)

6h

rt

OH

3:1

(77)

6h

66°

d.r. (76)

Time

SiMe2Ph

SiMe2Ph

(86), 94

Temp

n-Pr

OH

OH

88

138

138

159, 762

760

760

416

C5

n-Bu

O H

O H

Carbonyl Substrate

O B O

Bu-n

Bu-n

EtO2C

n-Bu

n-Bu

B

O O

B

O

B

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

B(OPr-i)2

B(OPr-i)2

R = CH2CO2Me

n-Bu

R

O

Allylborane Reagent

rt, 6-24 h

Sc(OTf)3, toluene,

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

18 h

THF, –78° to rt,

18 h

THF, –78° to rt,

–78°, 5 h

Conditions

I

OH

n-Bu

n-Bu

n-Bu

O

OH

Bu-n

Bu-n

Bu-n O

(78), 82

(62), 19:1 d.r.

(77), 71, 96:4 d.r.

(89), 95:5 d.r.

(81), 89:11 d.r.

CO2Me

I (83), 73, 97:3 d.r.

n-Bu

n-Bu

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

24, 26

740

740

772

772

90

Refs.

417

i-Pr

t-Bu

O

O

H

H

Ph

Cl

O

Ph

B

O

N

B(Pr-n)2

B[(–)-Ipc]2

B(OPr-i)2

B[(+)-Ipc]2

B[(–)-Ipc]2

"

B[(–)-Ipc]2

Cl ,

N

Neat, 60°

–78°, 3 h

2. Aldehyde, THF,

MeOB[(–)-Ipc]2,

Ph LDA,

1. Ph

Toluene, rt, 3 d

–100°

Ether, pentane,

3. Aldehyde

,

LiNCy2, THF, –78°

MeOB[(–)-Ipc]2, 2. BF3•OEt2

1.

rt, 24 h

Ether, –78°, 2 h;

2. H2O2, NaOH

4h

1. Ether, –78° to 0°,

i-Pr

i-Pr

t-Bu

t-Bu

t-Bu

t-Bu

t-Bu

OH

OH

N

OH

OH

OH

Cl

OH

Ph

Ph

(65)

(41), >95:5 d.r.

(60)

(88), 95

(65), 78

Bu-t

(59), >95, >97:3 d.r.

(34), 92, >20:1 d.r.

OH

OH

OH

238

746

741, 744

505

159

175

157

418

C5

i-Pr

O H

Carbonyl Substrate

Bu-n

EtO2C

Et

EtO2C

Bu-n

Bu-n

n-Bu

n-Bu

B

O O

O

O

O

O

O B

B

O

B

O

O

B

O

B

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Allylborane Reagent

rt, 6-24 h

Sc(OTf)3, toluene,

rt, 24 h

Sc(OTf)3, toluene,

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

Conditions

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

n-Bu

O

O

n-Bu

OH

OH

OH

n-Bu

OH

O

Et

O

Bu-n

Bu-n

(53), 19:1 d.r.

(46), >20:1 d.r.

(76), 66, 96:4 d.r.

(72), 63, 96:4 d.r.

(85), 72, 96:4 d.r.

(93), 84, 96:4 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

24, 26

26

740

740

740

740

Refs.

419

O

i-Pr

Et

HN Boc

H

H

O

O

Cl

R

R3Si

TMS

Cl

Cl

B

O

O

O

B

O O

B[(–)-Ipc]2

BEt2

BEt2

B

O

B[(+)-Ipc]2

B[(–)-Ipc]2

Ether, –95°, 4 h

–70° to 0°

rt, 3 d

Pentane, 4 kbar,

Neat, rt, 4 d

Neat, rt, 4 d

Ether, –95°, 4 h

Ether, –95°, 4 h

i-Pr

HO

HO

Et

Et

Et

Et

Et

HN

SiR3

TMS

Cl Boc

OH

R

OH

OH

OH

Cl

OH

Cl

OH

(66)

(50)

(70)

(79)

d.r.

75:25

72:28

d.r.

74:26

73:27

(61), 85:15 d.r.

(70)

t-Bu

TIPS

R

Et

Me

R

(82), 72:28 d.r.

(57), 95:5 d.r.

(59), 85:15 d.r.

651

732

539

539

539, 521

539

651

651

420

C5

HN

S

PhS

S

H

O

O

Boc

O

TBDMSO

PMBO

i-Pr

H

H

O H

O H

Carbonyl Substrate

O

B

O

OMe

OMOM

OSEM

OSEM

Cl

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

Allylborane Reagent

THF, –78°

THF, –78° to rt, 3 h

THF, ether, –78°

THF, ether, –78°

—

Ether, –95°, 4 h

Conditions

HN

Cl Boc

OH

O

OH

B

S

PhS

S

OMe

OH

OMOM

OH

(47)

(73)

OSEM (49), >95, >19:1 d.r.

TBDMSO

OH

O

(—)

(60), 99:1 d.r.

OSEM (60), >95, >97.5:2.5 d.r.

TBDMSO

PMBO

i-Pr

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

515

773

513

511

202

651

Refs.

421

O

OBn

H

TESO

OBn O

PMBO

t-BuO

O H

O H

n-Pr

PhMe2Si

PhMe2Si

PhMe2Si

OMOM

O

B

O

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

BR2

THF

—

—

3h

THF, –95° to rt,

–78° O

69 36

(+)-Ipc toluene 2-d-Icr TESO

SiMe2Ph

SiMe2Ph

77:16

(79) –78°

d.r. 69:19

(90) –30°

Temp

BnO n-Pr SiMe2Ph

OBn OH

OBn

OBn OH

OBn

OBn OH

83

85

85

>95

(79), 1:1 d.r.

(83), 9:1 d.r.

OMOM

OH

74

ether

77

(+)-Ipc CH2Cl2

Solvent Yield ee

B

(+)-Ipc ether

R

O

OH

(91), >10:1 d.r.

PMBO

t-BuO

O

760

774

774

458

203

422

C5

O

O

O

O

O O H

(i-Pr)2NMe2Si

OMe

B[(+)-Ipc]2

B[(–)-Ipc]2

–78°

–78°

12.5 h

THF, –78° to –23°,

2. KF, H2O2

1. Ether, –78°, 3 h

O

O

O

O

S

PhthN

O

O

O

O

d.r.

8:20

19:4

OH

OH

OH

OMe

OH

OMe

(73)

21:6

2:21

Syn:Anti

(44), >95:5 d.r.

(60), >99:1 d.r.

(79), >99:1 d.r.

OBn OBn OMOM

OBn OH

(86)

(85)

OMe R

(CH2)2OTBDMS

R

BnO

OH

Product(s) and Yield(s) (%), % ee TBDMSO

O O

B[(+)-Ipc]2

B[(–)-Ipc]2

O

—

O

OMe

OMOM

R

B

O

Conditions

O

H

H

O

OBn OBn

H

H

OBn O

OMe

O

Allylborane Reagent

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

O

O

S

PhthN

BnO

TBDMSO

Carbonyl Substrate

45

776

776

775

545

Refs.

423

C6

n-C5H11

O H

O H

OPh

OMe

TMS

Bu-n

EtO2C

Ph

PhMe2Si B

BBN

B(OBu-n)2

B(OBu-n)2

B

O

O

O

O

(i-Pr2)NMe2Si B[(+)-Ipc]2

O O

O

–

OPh

FB(OBu-n)2

–

OMe FB(OBu-n)2

—

rt, 16-24 h

Sc(OTf)3, toluene,

80°, 5 h

I Pd2(dba)3, EtOAc,

Ph

PhMe2Si B

2. KF, H2O2

1. Ether, –78°, 3 h

O

OH

n-C5H11

n-C5H11

OH

+

n-C5H11 II

OH

I + II (61), I:II = 3.5:1

I OPh

OH

(65)

(94), >95:5 d.r.

(45), 2.5:1 d.r.

(74), >99:1 d.r.

TMS

OMe

OH

(47), >95:5 d.r.

SiMe2Ph

O

Ph

OH

S n-Bu

S

S

OH

OPh

46

46

683

26

761

45

424

C6

n-C5H11

O H

Carbonyl Substrate

TMS

BCy2

B[(+)-Ipc]2

Ph2N

R

B[(–)-Ipc]2

Ph2N

OMEM

B[(+)-Ipc]2

Allylborane Reagent

THF

3h

THF, –78° to 0°,

3h

THF, –78° to 0°,

—

Conditions

Ph2N

OH

OMEM

Ph2N

3h 7h 4h 20 h

rt 50° 0° 50° reflux

n-Bu n-Bu CH2TMS CH2TMS CH2TMS

4h

52 h

6h

–15° n-Bu

rt

3h

rt

i-Pr

Time

Temp

(92)

(73)

(78)

(81)

(91)

(86)

(90)

H

OH

H

OH

(93)

n-C5H11

n-C5H11

Me

R TMS

+

+

NPh2

97:3

4:96

17:83

94:6

9:91

70:30

96:4

3:97

d.r.

(25)

NPh2

(25)

(59), 97, >99:1 d.r.

R

n-C5H11

OH

(40), >95, >95:5 d.r.

n-C5H11

OH

(43), >95, >95:5 d.r.

n-C5H11

n-C5H11

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

777

730, 731

730, 731

250

Refs.

425

+

(55) (79) (69)

NaOH NaOEt H2SO4

rt rt –15° rt 50°

BCy2 BBN BCy2 BCy2 BCy2 BBN

n-Bu n-Bu n-Bu n-Bu CH2TMS

reflux rt rt

BCy2 BBN BCy2

CH2TMS i-Pr i-Pr

0°

CH2TMS

50°

BCy2 BCy2

CH2TMS

rt

rt

4h

24 h

52 h

20 h

4h

4h

7h

3h

6h

4h

3h

3h

R TMS Temp Time

1

OH

I + II

Work-Up

I

H

II

(92)

(75)

(73)

(78)

(81)

(93)

(91)

(86)

(90)

(89)

(93)

(89)

72:28

29:71

41:59

I:II

II

3:97

96:4

I:II

n-C5H11

(70)

H2SO4 Bu-t

(81)

NaOH

Me

n-C5H11

n-C5H11

H

H n-C5H11 I + II

I

+

Work-Up

Bu-n

BBN

THF

THF, rt, 1 h

n-C5H11

H

Me

R2

BBN

THF, rt, 1 h

R2

R1

TMS

TMS

BBN

R1

TMS

t-Bu

n-Bu

3:97

88:12

94:6

83:17

6:94

>99:1

91:9

30:70

4:96

97:3

97:3

98:2

d.r.

Bu-t

Bu-n

777

736

736

426

C6

n-C5H11

O H

Carbonyl Substrate

BBN

BBN

BBN

BBN

TMS

TMS

TMS

TMS

i-Pr

TMS

Ph

Allylborane Reagent

THF, rt, 1 h

THF, rt, 1 h

THF, rt, 1 h

THF, rt, 1 h

Conditions

n-C5H11

H

n-C5H11

H

n-C5H11

H

n-C5H11

H

(67) (80) (84)

NaOH NaOEt H2SO4

(82) (65)

NaOEt H2SO4

I

H

(82) (85) (87)

KOH NaOEt H2SO4

H

I + II (73) (72) (65)

Work-Up NaOH NaOEt H2SO4

Pr-i

Ph

3:97

98:2

95:5

II I:II

0.5:99.5

97:3

97:3

II I:II

11:89

88:12

88:12

II I:II

n-C5H11

I + II

Work-Up

+

5:95

95:5

n-C5H11

(77)

NaOH

+

I + II

TMS

H

II I:II

96:4

n-C5H11

I + II

Pr-i

H n-C5H11

Work-Up

+

+

Work-Up

I

I

I

Ph

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

TMS

736

735, 736

736

736

Refs.

427

O

B

Ph

PhMe2Si

Bu-n

BEt2

BEt2

O

O

O

O

O

O B

B

O

B

O

O

R = TBDMS

Bu-n

RO

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

,

O O

O

,

,

–70° to 0°

80°, 5 h

I Pd2(dba)3, EtOAc,

Ph

PhMe2Si B

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

OH

HO

HO

n-C5H11

OH

n-C5H11 n-Bu

n-C5H11

OH

(73), 73, 96:4 d.r.

(75), 79, 96:4 d.r.

(86), 82

(83)

(67), >99:1 d.r.

SiMe2Ph

Bu-n

Ph

TBDMSO

n-C5H11

OH

732

761

740

740

88

428

C6

O

O

O

O

3

O

O

H

H

O H

Carbonyl Substrate

B

O

BBN

B[(–)-Ipc]2

B(OBu-n) 2

O

TMS

OMe

PhMe2Si

n-Pr

OPh

O

TMS

TMS

BBN

Allylborane Reagent

FB(OBu-n) 2

THF, –50°

OPh

–

Neat, 10 d

THF, rt, 1 h

2. NaOH

1. THF, rt, 1 h

Conditions

O I

O

O

O

O

OH

OPh

OH

OMe

H2SO4

KOH

Work-Up

+

n-Pr

OH

SiMe2Ph

(73), 83:10 d.r.

OPh

(77), 94:6 d.r.

(61)

(58)

I + II (50), I:II = 1.85:1

II

O

3

OH

TMS

(67)

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

760

46

47, 36

735, 736

736

Refs.

429

Br 3

TBDPSO

i-Pr

OH

O

O

O

O

O

O

H

H

OMe

H

O

H

O

B

RMe2Si

PhMe2Si

R

O OMe

B

O

B

O O

O

O

O

B[(–)-Ipc]2

O

OPr-i

OPr-i

O

–78°

4 Å MS, toluene,

–78°

OPr-i 4 Å MS, toluene,

OPr-i

OMe, i-Pr ether, –78° to rt, 1.5 h

OMe B O O

B(NMe2)2,

2. L.A., –78° to rt, 3 h

1.

— O

Br

(81) (78)

menthofuryl CyO

67:33

90:10

d.r. 90:10

(69)

SiMe2R

97.5:2.5

2-(5-methyl)furyl

OH

d.r. 98:2

R

3

O

(86), >99:1 d.r.

OMe SiMe2Ph

OH

(96)

B(OMe)3

78:22

d.r. 70:30

(98)

(—), 95

(—), 89

ZrCl4

OH

O O

O

R

OH

L.A.

TBDPSO

i-Pr

OH

(CH2)3

Ph

R

O

158

194, 758

299

343

430

C6

BnO

MeO

Br

N

3

O

O

H

H

OBn

O

O

H OPMB

O

H

Carbonyl Substrate

Ph

Ph

"

Ph

"

Ph

OTHP

N

N

RMe2Si

O

B[(–)-Ipc]2

O O

OPr-i

OPr-i

B[(+)-Ipc]2

B[(–)-Ipc]2

B

O

Allylborane Reagent

N

N

THF, –78°

–78°, 3 h

2. Aldehyde, THF,

MeOB[(+)-Ipc]2

Ph LDA,

1. Ph

THF, –78°

–78°, 3 h

2. Aldehyde, THF,

MeOB[(–)-Ipc]2

Ph LDA,

1. Ph

3h

THF, –78° to rt,

–78°

4 Å MS, toluene,

,

,

Conditions

N

H

I

N

OH

OBn

O

Ph

Ph

I

N Ph

Ph

I (51), 90, >95:5 d.r.

N

OH (51), 90, >95:5 d.r.

(49), 91, >95:5 d.r.

(52), >97.5:2.5 d.r.

OTHP OPMB

OH

96:4

(82)

d.r.

menthofuryl

SiMe2R (68) 90:10

OH

2-(5-methyl)furyl

R

3

O

I (49), 91, >95:5 d.r.

BnO

MeO

Br

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

160

746

160

746

778

158

Refs.

431

C7

Ph

O H

X

OPMP

OMOM

"

OMEM

OMe

OMe

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

X,

ether, –78°

MeOB[(+)-Ipc]2

LiNCy2,

3. Aldehyde

2. BF3•OEt2

1.

THF, –100°, 10 h

THF, –78°

THF, –78°, 10 h

THF, –100°

THF, –78°, 3 h

THF, –78°, 3 h

I OMEM

OH

OMe

OH

OMe

(71), 98

(75), 90, >99:1 d.r.

(72), 90, >99:1 d.r.

Ph

Ph

Ph

(75), 97 (68), 93

Br

94:6

98:2

d.r.

(76), 96, >99:1 d.r.

(62)

Cl

X

X

OH

OPMP

OH

OMOM

OH

I (—), 95, >99:1 d.r.

Ph

Ph

Ph

OH

159

407

779

388

407, 250

48

48

432

C7

Ph

O H

Carbonyl Substrate

B[(–)-Ipc]2

B[(+)-Ipc]2

Ph2N

B[(–)-Ipc]2

Ph2N

X

Cl

B[(+)-Ipc]2

Allylborane Reagent Cl,

ether, –78°

MeOB[(+)-Ipc]2,

LDA,

LiNCy2, –78°

MeOB[(–)-Ipc]2,

X,

3h

THF, –78° to 0°,

3h

THF, –78° to 0°,

3. Aldehyde

2. BF3•OEt2

1.

3. Aldehyde

2. BF3•OEt2 (x equiv)

1.

Conditions

THF ether

Cl Br

Ph2N

OH

ether

+

Solvent

Cl

X

X

OH

Cl

Ph2N (47), >95, >95:5

Ph

OH +

x

Ph H

OH

H

(12)

NPh2

(15)

NPh2

96:4

(77), 95

Ph

99:1

(77), 76

OH

98:2

d.r.

(—), 95

(—), 84

(78), 98

1.33

2.5

(48), >95, >95:5 d.r.

Ph

Ph

Ph

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

730

730, 731

159

159

Refs.

433 Cy

Ph

Ph

Ph

Ph

"

BR2

BEt2

BR2

BEt2

BEt2

OCOPh,

OCOPh,

4h

THF, –78° to rt,

45°, 21 h

THF, rt, 4 h;

BEt3, Pd(PPh3)4,

Ph,

OCOPh

THF, rt, 14 h

Ph BEt3, Pd(PPh3)4,

4h

THF, –78° to rt,

THF, rt, 14 h

Ph BEt3, Pd(PPh3)4,

OCOPh,

THF, rt, 23 h

BEt3, Pd(PPh3)4,

Ph

I Ph

Ph

Ph

Ph

Ph

Ph

Ph

Cy

OH

OH

OH

OH

Ph

I (83), 2.2:1 d.r.

Ph

OH

(84), 84

(–)-Ipc

(–)-Ipc

Cy

R (80), 80

(77), —

(76), 1.6:1 d.r.

(77), 2.3:1 d.r.

(90), —

Cy

R

(74), 2.3:1 d.r.

d.r.

4:1

96:4

d.r.

>99:1

>99:1

733

483

483

733

483

483

434

C7

Ph

O H

Carbonyl Substrate

Ph

Ph

Ph

Ph

N

N

n-C6H13

n-Bu

Cy

"

B[(+)-Ipc]2

B[(–)-Ipc]2

BR2

BR2

BCy2

Allylborane Reagent

N

THF, –78°

THF, –78°, 3 h

2. Aldehyde,

MeOB[(+)-Ipc]2

Ph LDA,

1. Ph

THF, –78°

4h

THF, –78° to rt,

4h

THF, –78° to rt,

CCl4, 0°

,

Conditions

N

OH

N

OH

I

Bu-n

Cy

R

(–)-Ipc

Cy

R

Ph

Ph

Ph

Ph

(52), 90, >95:5 d.r.

(53), 93, >95:5 d.r.

(81), 74

(82), —

(78), 78

(81), —

(—), 96:4 d.r.

C6H13-n (–)-Ipc

OH

OH

Cy

I (52), 90, >95:5 d.r.

Ph

Ph

Ph

Ph

Ph

OH

9:1

88:12

d.r.

88:12

87:13

d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

160

746

160

733

733

733

Refs.

435 Ph

O

Ph

Ph

B

O

O

Ph

PhMe2Si

B

O

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

(i-Pr)2NMe2Si

B[(–)-Ipc]2

B[(–)-Ipc]2

Ph

N

(i-Pr)2NMe2Si

Ph

N

2. H2O2, NaOH

4h

1. Ether, –78° to 0°,

Ether, –78°, 2 h

THF, –78°, 4 h

2. KF, H2O2

1. Ether, –78°, 3 h

2. KF, H2O2

1. Ether, –78°, 3 h

THF, –78°, 3 h

2. Aldehyde,

MeOB[(–)-Ipc]2

Ph LDA,

1. Ph

,

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Ph

B

Ph

O Ph

SiMe2Ph

OH

OH

Ph

O

OH

OH

OH

OH

OH

OH

N

OH

(76), >95, >97:3 d.r.

(—)

(81), 93

(47), >95:5 d.r.

(50), >95:5 d.r.

(53), 93, >95:5 d.r.

157

175

734

45, 752

45, 752

746

436

C7

Ph

O H

Carbonyl Substrate

X

O

O

B

O

B

O

B[(+)-Ipc]2

B[(–)-Ipc]2

"

"

B[(–)-Ipc]2

Allylborane Reagent

Cl, LiNCy2, ether

MeOB[(–)-Ipc]2,

3. Aldehyde

2. BF3•OEt2 (x equiv)

1.

rt, 24 h

Ether, –78°, 2 h;

2. H2O2, NaOH

4h

1. Ether, –78° to 0°,

rt, 24 h

Ether, –78°, 2 h;

Ether, –78°, 2 h

Conditions

Ph

Ph

Ph

Ph

Ph B

III

OH

I X

OH

OH

Ph

O

OH

OH

OH

O

OH

OH

X

+

Ph

(40), 93, >20:1 d.r.

Ph

Ph

II X

OH +

(42), 95, >20:1 d.r.

(80), >95, >97:3 d.r.

OH

(—)

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

159, 762

175

157

175

175

Refs.

437

X

X = Cl

"

X = Cl, Br

BBN

–78° –95° –95° –95° –95° –95° –95° to –78° –95° to –78°

2.63 2.63 2.65 2.65 1.33 1.66 2.63 1.33

LDA, THF

MeOBBN,

X,

–78°

Cl, LiNCy2, THF

MeOBBN,

3. Aldehyde

2. BF3•OEt2 (x equiv)

1.

3. Aldehyde

2. BF3•OEt2

1.

Temp

x 2.63 99:1 98:2 >99:1 >99:1 >99:1 >99:1 >99:1

Cl Br Cl Cl Cl Cl Cl

–78° –95°

Br Cl

–95° –95° to –78° –95° to –62° –95° to –41° –95° –95°

1.33 1.33 1.33 1.33 1.5

(77)

(76)

(79)

2.63

Temp x

I + II + III, II:I = 99:1

–78°

II:I

99:1

99:1

99:1

99:1

99:1

94:6

99:1

9:1

91:9

91:9

88:12

85:15

II:(I+III)

85

86

97

98

87

86

88

74

78

II % ee

96:4

>99:1

>99:1

99:1

99:1

95:5

(I+II):III

I + II + III

96:4

Br

Temp

98:2

Cl

Cl

X

I + II + III

(I+II):III

X

159

159

438

C7

Ph

O H

Carbonyl Substrate

TMS

n-Bu

t-Bu

TMS

TMS

TMS

BBN

BBN

BBN

B[(+)-Ipc]2

Allylborane Reagent

THF, rt, 1 h

THF, rt, 1 h

THF, rt, 1 h

–100°

Ether, pentane,

Conditions

Ph

H

Ph

H

Ph

H

Ph

I + II (88) (83)

Work-Up KOH H2SO4

I

(75)

H2SO4

+

(81)

TMS

I + II NaOH

Ph

H

Ph

H

(68)

H2SO4

+

(83)

NaOEt

Bu-n

(70)

I:II

2:98

98:2

I:II

II

2:98

98:2

TMS

Bu-n

62:38

29:71

41:59

I:II

Bu-t

II

II

NaOH

Ph

H

I + II

+

Work-Up

Bu-t

(92), 95

Work-Up

I

I

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

735, 736

736

736

505

Refs.

439 B

O

TMS

TMS

OMe

i-Pr

Ph

TMS

O

BBN

BBN

BBN

OMe, Cl

–

THF, rt, 1 h

THF, rt, 1 h

THF, rt, 1 h

O B

O

Ph

Ph

H

Ph

H

Ph

H

(84)

H2SO4

OMe

H

Ph

H

Ph

II

Ph

II 91:9

I:II

Pr-i

<0.5:99.5

>99.5:0.5

I:II

II

2:98

98:2

I:II

11:89

H

Ph

(95)

(85)

NaOH

OH

I + II

Work-Up

I

(56)

H2SO4

+

(58)

NaOH

Pr-i

I + II

Work-Up

I

(69)

H2SO4

+

(71)

NaOH

Ph

I + II

I Work-Up

+

46

736

736

736

440

C7

Ph

O H

Carbonyl Substrate

O

OTHP

OTHP

B

O

B

O

B

O

B

O

B

O

OMe

OMOM

OMEM

OMe

B

O

O

O

O

O

O

O

Allylborane Reagent

O

Neat, rt

—

Neat, rt, 48 h

Neat, 60°, 4 h

Cl

O B

– OMOM,

Neat, 20°, 2 d

Conditions

I

OTHP

OH

OMOM

OH

OMEM

OH

OMe

Ph O

OH

OMe

I (70-80), 93:7 d.r.

Ph

Ph

Ph

Ph

OH

(93), 94:6 d.r.

(70-80), 93:7 d.r.

(82), >95:5 d.r.

(59)

(86), >95:5 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

47, 36

104

34

47, 36

46

36

47, 33,

Refs.

441

B

O

B

O

O

O

TMS

O

B

TMS O

TBDMSO

O

MeO

OPh

OPh

O

O B

O

B

O

O B

O

O

—

rt, 2 d

Petroleum ether,

20°, 36 h

Petroleum ether,

O – B O OPh, Cl

O – B OPh, Cl O

Neat, 20°, 2 d

+

TMS

Ph

Ph

Ph

OTBDMS

OH

O

OH

OMe

OH

Ph II

OH

(98), >95:5 d.r.

I + II (80), I:II= 4.7:1

I OPh

OH

O

(67), 96:4 d.r.

TMS

(92), 94:6 d.r.

(87), 95:5 d.r.

I + II (69), I:II = 3.3:1

Ph

Ph

OH

OPh

780

47

47, 33

46

46

47

442

C7

Ph

O H

Carbonyl Substrate

SR

"

O B

1.0 0.65

30:70

B

O

Equiv

Z:E

O

O

O

O

O

>95:5

B

O

B

O

R = TBDMS

SiMe2Ph

AcO

RO

O

O

OEt

OEt

O

OPr-i

OPr-i

Allylborane Reagent

O OAc

O 2

OEt

OEt

O

O

CH2Cl2, rt

octane, 50°

Pt(C2H4)(PPh3)2,

,

PhMe2Si B

—

toluene, 20°, 21 h

OAc, Pd2(dba)3, DMSO,

O B

O

–78°, 5 h

4 Å MS, toluene,

,

Conditions

OTBDMS

I

OH

SiMe2Ph

(63), 95:5 d.r.

5:95

(95) Et

d.r. 98:2

(95)

SR

(59), 45

(82), 67

Me

R

OH

OAc

OH

I (85)

Ph

Ph

Ph

Ph

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

72

781

737

349

88

Refs.

443 R

Br

Ph

B

O

B

O

B

O

O

O

O

O

O

OEt

OEt O 2

OAc,

O

OEt

OEt

O

CH2Cl2, 40°

R

O B O R,

,

5 2 5 2

BnO Cl Cl

2. Aldehyde, rt

x BnO

R

Br

2

5

x (72)

(73)

(79)

(78)

(63)

(60)

(44-67)

(83), 43

CH2Cl2, 40°

R

OH

OH

Ph

5

Ph

Ph

Ph

OH

TBDMSO

Mes N N Mes Cl Cl Ru PCy3 Ph (x mol%),

1.

, Br,

Mes N N Mes Cl Cl Ru PCy3 Ph (x mol%),

Br

O B

2. Aldehyde, rt

1.

toluene, 20°, 21 h

Pd2(dba)3, DMSO,

Ph

O B

O

d.r.

4.6:1

4.9:1

3.2:1

4.7:1

4:1

d.r.

3.6:1

3.8:1

184

184

349

444

C7

Ph

H

x equiv

O

Carbonyl Substrate

B O

O

B O

O

OCH(Pr-i)2

OCH(Pr-i)2

O

OPr-i

OPr-i

O

O

B

N

O

O

B

Ac

Cl

O

R = CH2CO2Me

AcO

Cy

R

O

O

Allylborane Reagent

AcO

(y equiv),

O B O OAc,

2. Aldehyde, rt

Mes N N Mes Cl B Cl Ru Ph, PCy3 CH2Cl2, 40°

PCy3 A Cl Ru Cl PCy Ph, 3

1.

Neat, 60°, 5 h

(10:3), –100°

Toluene/pentane

–78°, 5 h

Conditions

Ph

Ph

Ph

Ph

3

3

1.5 0.75

3

1.5

0.5

3

1.5

1.5

OAc y

Cy

B

B

B

B

A

Cat.

(80), 83

(30), 49

(52)

Cl

CO2Me

x

OH

Ac

N

OH

OH

OH

(75)

(57)

(75)

(75)

(32)

4.5:1

4.7:1

4.5:1

4.5:1

1.8:1

d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

184

178

738

90

Refs.

445 i-Pr

i-Pr

TMS

O

O

O

B

O

B

O

B

O

O

O

O

B O

O

O

O ,

O B ,

O B

O B

2. Aldehyde, 24 h

–15° to rt

O i-PrMgCl, THF,

1.Cl

2. Aldehyde, rt, 24 h

–15°, 30 min

,

O i-PrMgCl, toluene,

1. Cl

Ether, rt, 1-3 d

,

I Pr-i

TMS

I (30), 99:1 d.r.

Ph

OH

OH

(69)

2

2. Aldehyde, rt

(44), >99:1 d.r.

(89)

>20:1

d.r. >20:1

(68)

5

O

x

O

CH2Cl2, 40°

Ph

Ph

OH

(x mol%),

Mes N N Mes Cl Ru Cl PCy3 Ph

1.

87

87

32

184

446

C7

Ph

O H

Carbonyl Substrate

R2

Bu-n

n-Bu

n-Bu

R1

B

O

B

O

O

O

O

O

O

B(OPr-i)2

B

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

Allylborane Reagent

R2

,

(x equiv),

O

CH2Cl2, 40°

(y mol%),

Mes N N Mes Cl Cl Ru PCy3 Ph

R1

O B

18 h

THF, –78° to rt,

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

2. Aldehyde, rt

1.

Conditions

H

2-BrC6H4

OH

Ph n-Bu

OH

Bu-n

H

2-BrC6H4

10

5

20

20

(35) (51) (17) (49) (58) (34) (66) (45) (25) (60)

5 5 2 5 5 5 5 5 5 5

y

(96), 88:12 d.r.

(96), 40, 96:4 d.r.

(99), 37, 98:2 d.r.

H

2-BrC6H4

OH

H

Ph

10

—(CH2)5—

20 10

H

Me2COH

20

—(CH2)4—

H

Me2COH

5

x

3

H

—(CH2)4—

R2

t-Bu

R1

R1

R2

Ph n-Bu

Ph

Ph

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

772

740

740

184

Refs.

447 MeO

OMe

Bu-n

n-Bu

n-Bu

B

O

O

O

O

O

B

O O

O

B(OPr-i)2

B

O

B

O

B

O

O

OCH(Pr-i)2

OCH(Pr-i)2

B(OPr-i)2

72 h

4 Å MS, toluene, –78°,

Toluene, rt, 0.5 h

9d

Petroleum ether, 20°,

2d

Petroleum ether, 20°,

Neat, rt, 5-8 d

Neat, rt, 5-8 d

THF, –78° to rt, 18 h I

Bu-n

Ph

Ph

Ph

Ph

OH

OH

MeO

OH

MeO

OH

Ph n-Bu

OH

I (71), 99:1 d.r.

Ph

OH

(89), 38

(85)

(70), 90:10 d.r.

(55), 73:27 d.r.

(69), 93:7 d.r.

(95), 97:3 d.r.

741

741, 744

739

739

55

55

772

448

C7

Ph

O H

Carbonyl Substrate

B

O

B

O

O

O

B

O

B

O

B

O

O

O

O

O

O

O

B

O O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

OCH(Pr-i)2

OCH(Pr-i)2

Allylborane Reagent

O

O

,

O

,

Pd(PPh3)4

,

, O (CH2)2CH=C(Me)2

HB

Pd(PPh3)4

HB

—

–78°, 72 h

4 Å MS, toluene,

–78°, 72 h

4 Å MS, toluene,

–78°, 72 h

4 Å MS, toluene,

Conditions

I

I

OH

Ph

OH

I (89)

Ph

Ph

OH

I (90), 49

Ph

OH

(77)

(80), 9:1 d.r.

(95), 43

(86), 37

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

550

550

52

741

741

741

Refs.

449

B

O

B O

O

O

MeO2C B

O O

O

R = (+)-menthyl

RO2C

MeO2C

O

OEt OEt

(83) (87)

7d 4d 1d

rt 70° 100°

THF toluene

0° –25° –78° –25° 0° 0° 0° 0° 0° 0°

DMF/THF DMF/THF DMF/THF THF THFb CH2Cl2 4 Å MS, CH2Cl2 toluene 4 Å MS, toluene

rt

DMF

Temp

DMF

I

2d

2d

2d

2d

2d

2d

7d

6d

6d

3d

2d

Time

98:2 98:2 98:2

(74), 25 (76), 12

98:2

(75), 22

98:2

98:2

(56), 21

(67), 22

94:6

(40), 20

98:2

96:4

(76), 25

(64), 16

95:5

(52), 27

(69), 19

94:6

(80), 26

d.r.

87:13

85:15

d.r. 84:16

(64)

Time

Temp

Solvent THF

I

O

I (50), 25, 87:13 d.r.

Ph

Solvent

See table

THF, rt, 5 d

See table

O

782

782

782

450

C7

Ph

O H

Carbonyl Substrate

Et

O

B

B

O

B

O

B

O O

O

O

O

Ph

EtO2C B

O O

R = (–)-8-phenylmenthyl

RO2C

EtO2C

MeO2C

Allylborane Reagent

O

O

,

,

L.A., rt, 6-24 h

2. pTSA

1. Neat, rt, 14 d

Pd(PPh3)4

HB

16-120 h

Toluene, 80°,

See table

Conditions

toluene

THF

I Solvent

Ph

Ph

Ph

I

O

O

OH

Et

O

O

toluene toluene

Yb(OTf)3

toluene Cu(OTf)2

Sc(OTf)3

Solvent CH2Cl2

Sc(OTf)3

(80), 8

(75), 10

L.A.

(55), >95

3d

7d

Time

(81)

100°

rt

Temp

I (60), >20:1 d.r.

Ph

O

O

(91)

(67)

(93)

(72)

83:17

79:21

d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

24, 26

59

550

59, 26

782

Refs.

451

x equiv

"

SiMe2Ph

B

4h 8h 4h 4h

80° 50° 80° 80° I (87)

2h

120°

CH2Cl2, rt

Time

SiMe2Ph Temp

I

Pt(C2H4)(PPh3)2,

Ph

TfOH

TfOH

Sc(OTf)3

TfOH

TfOH

Tf2NH

CF3CO2H

none

Catalyst

CO2R

octane

,

2.0

(–)-menthyl

O

1.5

(–)-menthyl

OH

0.9

(–)-menthyl

,

0.9

(–)-menthyl

O

0.9

Me

O

0.9

Me

O

0.9

Me

PhMe2Si B

x

Ph

OH

0.9

O

Catalyst, toluene

I (89), >20:1 d.r.

Me

B

O

Toluene, rt, >12 d

R

RO2C

"

(85)

(63)

(61)

(78)

(74)

0°

0°

0°

0°

rt

rt

rt

rt

Temp

96:4

93:7

98:2

95:5

81:19

d.r.

16 h

16 h

16 h

16 h

24 h

24 h

24 h

24 h

Time

(99)

(96)

(<5)

(78)

(99)

(99)

(77)

(<5)

72

781

30

59, 26

452

C7

Ph

O H

Carbonyl Substrate

Cy

O

B

BBr(Thex)

BBrCy

O

O

PhMe2Si B

O

3. NaOH, H2O2

–78° to 0°, 1 h

HBCy2, n-Bu4NBr,

Br ,

–78° to 0°, 1 h

n-Bu4NBr,

HB(Thex)2,

Br ,

2. Aldehyde, 0° to rt, 1 h

1.

2. Aldehyde, 0° to rt, 1 h

1.

Pt(C2H4)(PPh3)2, octane, 80°

,

2. Aldehyde, –78°, 3 h

benzene, rt

2

OEt ,

Pt(dba)2, PCy3,

,

,

2

O

OEt

O

O

O B

O

O

OEt

OEt

1.

O

Conditions

SiMe2Ph

B

O

Allylborane Reagent

Ph

OH

OH

Ph

Ph

OH

Cy

OH

PhMe2Si

Ph

OH

(40), >98:2 d.r.

(68), >98:2 d.r.

(60), 99:1 d.r.

(65), 33, >19:1 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

680

680

781

185

Refs.

453

R

c-C5H9

BBrR

BBr(siamyl)

BBr(C5H9-c) –78° to 0°, 1 h

n-Bu4NBr,

HB(C5H9-c)2,

Br ,

–78°, time 1

n-Bu4NBr (x equiv),

HBR2,

Br ,

Cy Cy

2h 2h 3h 3h 3h

12 h 1h 1h 12 h 12 h

none 0.1 none none 0.1

1h

2. Aldehyde, 0° to rt,

–78° to 0°, time 1

n-Bu4NBr,

HB(siamyl)2,

Br ,

Cy

1.

Cy

2h

2h

none

OH

siamyl

siamyl

siamyl

R

2h

x 0.5 h

R

OH

C5H9-c

Time 1 Time 2

Ph

Ph

Ph

OH

none

time 2

2. Aldehyde, 0° to rt,

1.

1h

2. Aldehyde, 0° to rt,

1.

15 h

1h

Time 1

(46)

(26)

(1)

(85)

(73)

(63)

(22)

(38)

(13)

(45), >98:2 d.r.

d.r. >98:2

>98:2

680

751

751, 680

454

C7

O 2N

Ph

O H

O H

Carbonyl Substrate

AcO

Ph2N

R

B

O O

B[(–)-Ipc]2

BR3– M+

Allylborane Reagent

OAc

2

toluene, 20°, 91 h

OAc, Pd2(dba)3, DMSO,

O B O

3h

THF, –78° to 0°,

– , M+ BR3, –70°, 1 h

Conditions

THF ether, HMPA (83) ether ether

Li Li Li Li

Et Et n-Bu s-Bu

O2N

O2N

I

H

OH

OAc

(74)

d.r.

61:39

83:17

83:17

83:17

50:50

82:18

NPh2

(85)

(11), >95, >95:5 d.r.

OH

(—)

NPh2

+

(91)

MgBr ether

Et

OH

(95)

ether

Li

(89)

(90)

Solvent

M

Et

R R

O2N

Ph

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

349

730

783

Refs.

455 EtO2C

Ph

AcO

B

O

B O

B

O

O

O

O

O

O

OEt

OEt

O OAc

O 2

OEt

OEt

2

, OAc,

, OAc

2

toluene, 20°, 24 h

CO2Et, Pd2(dba)3, DMSO,

O B O

40°, 21 h

Pd2(dba)3, DMSO,

Ph

O B O

toluene, 20°, 21 h

OAc, Pd2(dba)3, DMSO,

O B

O

O2N

O2N

I (67), 50

Ph

CO2Et

OH

OH

(75), 8:1 d.r.

(86), 33:1 d.r.

349

349, 636

349

456

C7

O 2N

O H

Carbonyl Substrate

R

AcO

H2N(O)C

O B O

B

O

B

O

O

O

Allylborane Reagent

, OAc

2

2

,

, OAc,

2

R Pd2(dba)3, DMSO

O B O

OAc, OAc Pd2(dba)3

O B O

toluene, 20°, 21 h

C(O)NH2, Pd2(dba)3, DMSO,

O B O

Conditions

OAc

40°

21 h 21 h 21 h 91 h

C6H4OMe-p CO2Et C(O)NH2 OAc

20°

20°

40°

Temp

Time R

O2N

R

OH

93 h

DMSO, toluene 20°

DMSO

21 h

Temp Time

OH

(74)

(61)

(75)

(83)

349

d.r.

>99:1

8:1

8:1

10:1

636

636 —

(69)

349

Refs.

(59) >99:1

d.r.

(61), 8:1 d.r.

40°

Solvent

O2N

O2N

C(O)NH2

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

457 Ph

EtO2C

Ar

MeO2C

R

MeO2C

B

O

O

O

B

O

B

O

O

,

CO2Me,

2

Pd2(dba)3, toluene, rt

R

OAc

O B O

16-120 h

Toluene, 60-80°,

rt, 24 h

BF3•SiO2, toluene,

rt, 2 d

2. BF3•OEt2 (30 mol%),

1.

O2N

O2N

O2N

(68) (69) (56) (64)

1-Nph 2-ClC6H4 2-furyl n-C8H17

Ph

(26)

(84)

4-MeOC6H4

O

(73)

4-ClC6H4

O

(80)

4-MeC6H4

Ar

Ar

CO2Me

(59)

OH

(81)

n-C8H17

CO2Me

Ph

R

R

OH

26

785

784

458

C7

O2N

O H

Carbonyl Substrate

EtO2C

Ph

O

O

O

O

B

–K+

B

O

B

BF3

CO2Me

Bu-s

EtO2C

Bu-n

EtO2C

n-Bu

TBDPSO

EtO2C

O

B

O O

Allylborane Reagent

rt, 5 h

CH2Cl2/H2O (1:1),

n-Bu4NI (0.1 equiv),

Toluene, rt, 12 d

CH2Cl2, 40°, 48 h

16-120 h

Toluene, 80°,

16-120 h

Toluene, 80°,

Conditions

O2N

O2N

O2N

O2N

O2N

OH

(75), >20:1 d.r.

(89)

(26), 15:1 d.r.

(67), >20:1 d.r.

(76), >20:1 d.r.

CO2Me

O

O

Bu-n

O

OTBDPS

O

Ph

s-Bu

O

n-Bu

O

O

O

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

784

59

59, 26

59, 26

59, 26

Refs.

459

R

MeO

O H

O H

EtO2C

Ph

MeO2C

allyl

EtO2C

Bu-i

EtO2C

Et

O

B

O

B

O

B

O

O

O

O B O

Catalyst, toluene

Toluene, 110°, 16-24 h

Toluene, 110°, 16-24 h

Toluene, 110°, 16-24 h

R

rt

Sc(OTf)3 BF3•OEt2 BF3 BF3 none BF3

O2N O2N O2N H MeO Cl

rt

90°

rt

rt

rt

rt

none

24 h

48 h

48 h

24 h

(78)

(62)

(67)

(83)

(81)

(48)

62 h 48 h

(74)

192 h

Time

(48)

(65), >20:1 d.r.

(55), 20:1 d.r.

allyl

Temp

Catalyst

Ph

CO2Me

O

Et

O

R

OH

O

i-Bu

O

Et

O

O2N

MeO

MeO

MeO

O

785

59, 26

59, 26

59, 26

460

C7

R

1

O H

Carbonyl Substrate

Et

EtO2C

R2

PhMe2Si

B

O

B

O

O

O

Allylborane Reagent

,

16-120 h

Toluene, 80°,

80°, 5 h

I Pd2(dba)3, EtOAc,

R2

O O O

PhMe2Si B

,

,

Conditions

R1

R

1

Ph Ph 4-MeC(O)C6H4 4-MeOC6H4 4-EtO2CC6H4 n-Bu Cy c-Pr

MeO Cl H H H H H H

MeO (70)

O2N (81) >20:1

d.r. 19:1

R1

Et

O

Ph

H

O

R2

SiMe2Ph

R1

R2

OH

>99:1 >99:1 >99:1 >99:1 >99:1 95:5 97:3 97:3

(55) (92) (86) (87) (70) (92) (75) (85)

d.r. >99:1

(96)

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

59, 26

761

Refs.

461 R2

R2 R3

EtO2C O

O

Me n-Bu Me n-Bu n-Bu n-Bu

Et Me Et Me Et Me

AcO O2N MeO MeO MeS Me

12 h

2. BR23, –78° to rt,

30 min

LDA, THF, –78°,

,

OH

R1

R2 Et n-Bu Et Et Et

R1 H H Me MeO O2N

I

R1

R2

(93)

(81)

(92)

(92)

(89)

+

d.r.

>20:1

2.5:1

1.8:1

2:1

>20:1

>20:1

>20:1

d.r. 76:24 88:12 64:36 86:14 82:18

100:0 100:0 92:8 100:0

R2 I:II

II

OH

(40), >95

(55), >95

(75)

(69)

(39)

(66)

(58)

(57)

(62)

91:9

Br

1. PhSe

H

R

2. pTSA, 4 h

I + II

Me

Me

O

R3

R2

R1 Br

O

R3

B R1

R1

R2

O

1. Toluene, rt, 14 d

rt, 6-24 h

Sc(OTf)3, toluene,

O

O O

Ph

B–R22SePh

O

Ph

B

O

692

26

26

462

C7

O

O

MeO

MeO

I

R

OMe

Br

OMe

O

O

O

Br

O

H

H

H

H

Carbonyl Substrate

B

O

MeO2C

Bu-n

EtO2C

SiMe2Ph

Ph

O

1. Toluene, 110°, 2 d 2. pTSA, rt, 6 h

B

Ether, –78° a

rt, 6-24 h

Sc(OTf)3, toluene,

octane, 120°

Pt(C2H4)(PPh3)2,

,

O PhMe2Si B Ph O ,

Conditions

O O

B[(+)-Ipc]2

B

O

O

Allylborane Reagent

O

O

MeO

MeO

I

R

OMe

Br

OMe

O

Br

OH

n-Bu

O

(74)

(97), 90, 4:3 d.r.

(55), 19:1 d.r.

99:1

(83)

2-MeO

O

99:1

(77)

4-MeO

d.r. 99:1

(79)

O

SiMe2Ph

Ph

H

R

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

30

786, 787

24, 26

781

Refs.

463

F

F

F

F

F

O H

MEMO

OMEM

OMEM

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

"

–100°

Pentane/ether (1:1),

24 h

THF, –100° to –78°,

—

toluene, 0°, 16 h

TfOH (20 mol%),

F

F

F

F

F

F

F

F

F

F

OMEM

OH

F

OMEM

OH

(65), 95, >19:1 d.r.

F

F

F (65), 95, >95:5 d.r.

F

O

OMEM

OH

OMe

O

(59), 97, >99:1 d.r.

MeO

MeO

Br (57), >19:1 d.r.

249

491

250

30

464

C7

Cy

F

F

O H

F

F

F

O H

Carbonyl Substrate

X

X

Bu-n

EtO2C

Ph

MeO2C

O

O

B[(–)-Ipc]2

BBN

B

O

B

O

Allylborane Reagent

X, MeOBBN

X,

LiNCy2, ether, –78°

MeOB[(–)-Ipc]2,

3. Aldehyde

2. BF3•OEt2

1.

3. Aldehyde

THF

2. LDA, BF3•OEt2,

1.

rt, 6-24 h

Sc(OTf)3, toluene,

24 h

BF3, toluene, rt,

Conditions

Cy

Cy

F

F

F

F

X

Br

Cl

X (71), 94

(72), 95

95:5

89:11 –95°

Cl

(76)

II:(I+III)

II X

–78°

(78)

Cy

OH

94:6

98:2

d.r.

+

(53), 19:1 d.r.

(87)

Br

X

+

O

Bu-n

Ph

CO2Me

Temp

III

F

O

F

OH

X

OH

Cy

OH

I X

OH

F

F

F

F

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

159, 762

159

24, 26

785

Refs.

465 Ph

Ph

Cl

X

Ph

Ph

N

N

"

"

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

X,

Cl,

base, ether, –78°

MeOB[(+)-Ipc]2,

N

N

THF, –78°

–78°, 3 h

2. Aldehyde, THF,

MeOB[(+)-Ipc]2,

Ph LDA,

1. Ph

THF, –78°

–78°, 3 h

2. Aldehyde, THF,

MeOB[(–)-Ipc]2,

Ph LDA,

1. Ph

3. Aldehyde

2. BF3•OEt2

1.

3. Aldehyde

,

,

LiNCy2, ether, –78°

MeOB[(+)-Ipc]2, 2. BF3•OEt2

1.

I

N

OH

Cl

Ph

Ph

97:3

93

LiCy(Pr-i)

(56), 91, >95:5 d.r.

>99:1

94

LiTMP

d.r. 97:3

96

I

N Ph

Ph

95:5

% ee

(61), 93, >95:5 d.r.

I (61), 93, >95:5 d.r.

Cy

OH

d.r. 98:2

LDA

(70), 94

(78), 96

Base

Br

Cl

X

I (56), 91, >95:5 d.r.

Cy

X

OH

(—)

Cy

Cy

OH

160

746

160

746

159

159

466

C7

Cy

O H

Carbonyl Substrate

Ph

O

Ph

Ph

B

O

O

Ph

PhMe2Si

B

O

(i-Pr)2NMe2Si

"

"

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

Allylborane Reagent

2. H2O2, NaOH

4h

1. Ether, –78° to 0°,

Ether, –78°, 2 h

Ether, –78°, 2 h

THF, –78°, 4 h

2. KF, H2O2

1. Ether, –78°

2. KF, H2O2

1. Ether, –78°, 3.5 h

Conditions

I OH

Cy

Cy

Ph

Cy

Cy

B

B

O

Ph

O Ph

SiMe2Ph

OH

OH

O

OH

Ph

O

OH

OH

I (63), >95:5 d.r.

Cy

OH

(70), 94, >97:3 d.r.

(—)

(—)

(85), 91

(45), >95:5 d.r.

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

157

175

175

734

45

752

Refs.

467

O

O

O

B

O

B

O

RMe2Si

B

O

B

O

O

O

O

O

R = TBDMS

Cl

n

B

O

B

R = CH2CO2Me

RMe2Si

RO

R

Ph

O

O

O

O

O

O

OPr-i

OPr-i

O

OPr-i

OPr-i

OPr-i

OPr-i

O

–78°, 5 h

2. Aldehyde, rt, 24 h

–15°, 30 min

–78°

4 Å MS, toluene,

–78°

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

OCH(Pr-i)2 Toluene/pentane (10:3), –100° O

OCH(Pr-i)2

O

OPr-i

OPr-i

O B

O PhMgCl, toluene,

1. Cl

,

Cy

Cy

Cy

Cy

Cy

Cy

n

Ph

Cl

OH

OH

SiMe2R

SiMe2R

(80), 97

(82), 98

(85), 91

2

1

n

(60), 65

(49), >99:1 d.r.

Ph

CyO

R (88), 87

(95), 72

menthofuryl

(87), 81

2-(5-methyl)furyl (83), 82

R

CO2Me

OTBDMS

OH

OH

OH

OH

158

158

88

738

90

87

468

C7

Cy

O H

Carbonyl Substrate

Bu-n

n-Bu

Ph

Ph

O

O

O O

O

B(OPr-i)2

B

O

OEt

OEt

O

OCH(Pr-i)2

OCH(Pr-i)2

B(OPr-i)2

B(OPr-i)2

B

O

B

O

O

Allylborane Reagent

O O OAc,

2

OEt

OEt

O B O

–78°, 72 h

4 Å MS, toluene,

rt

18 h

THF, –78° to rt,

18 h

THF, –78° to rt,

2. Aldehyde, rt, 24 h

–15°, 24 h

PhMgCl, THF,

1. Cl

toluene, 20°, 69 h

,

Conditions

Pd2(dba)3, DMSO,

Ph

O B

O

OH

OH

OH

Cy

Cy

OH

OH

Cy n-Bu

Cy

Cy

Cy

OH

Bu-n

Ph

Ph

4h 1h

neat (94), 89

30 h toluene

Time CH2Cl2

Solvent

(84), 95:5 d.r.

(82), 89:11 d.r.

(36), 96:4 d.r.

(77), 53

(90)

(91)

(91)

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

741

744, 741

772

772

87

349

Refs.

469 O OEt

O

O

EtO O

B

O

B

B

O OEt

O

O

O

O

O

OEt

O

O

SiMe2Ph

Ph

B

O

B

O

O

O

OPr-i

OPr-i

O

OCH(Pr-i)2

OCH(Pr-i)2

O

O

,

O 2

benzene, 80°

Pt(C2H4)(PPh3)2,

O

OEt

OEt

,

3. NaOH, H2O2

2. Aldehyde, –78°, 3 h

1.

O B

O

octane, 120°

Pt(C2H4)(PPh3)2,

,

Ph

PhMe2Si B

–78°, 72 h

4 Å MS, toluene,

–78°, 72 h

4 Å MS, toluene, I

Cy

Cy

OH

OH

I (94), 84

Cy

OH

(60), 96:4 d.r.

OH

(65), 74, >19:1 d.r.

SiMe2Ph

Ph

(92), 90

185

781

741

741

470

C7

Cy

O H

Carbonyl Substrate

Et

O

Cy

O

B

O

B

O

O

O

O

B

O

2

2

OR

OR

O

OEt

OEt

O

O

,

O

benzene, rt

2

OEt

Pt(dba)2, PCy3,

O B

OEt

I

CH(Pr-i)2

Et

Me

R

OH

Pr-i

I

OH

Et

Pt(dba)2, PCy3,

,

2

OR O

Cy

Cy

O

O

3. NaOH, H2O2

(17), 60

(38), 58

(68), 74

(21), 72

(72), 74, >19:1 d.r.

(54), 19:1 d.r.

(32), >20:1 d.r.

Product(s) and Yield(s) (%), % ee

benzene, rt

O

OR

2. Aldehyde, –78°, 3 h

1.

O B

O

3. NaOH, H2O2

2. Aldehyde, –78°, 3 h

1.

O

60°, 16 h

Cu(OTf)2, toluene,

O

rt, 24 h

Sc(OTf)3, toluene,

EtO2C

O n-Bu O

O B

Conditions

Bu-n

EtO2C

Allylborane Reagent

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

185

185

24, 26

26

Refs.

471

n-C6H13

O H

Si

Cy

B

O

Me

SiMe2Ph

Ph

PhMe2Si

CyO

Me

O

(i-Pr)2NMe2Si

O

BBrCy

B

O

B

O

O

O

O

2. KF, H2O2

1. Ether, –78°, 3 h

,

–78° to 0°, 1 h

HBCy2, n-Bu4NBr,

Br ,

octane, 120°

1h

2. Aldehyde, 0° to rt,

1.

O

O

Pt(C2H4)(PPh3)2,

,

Ph

PhMe2Si B

OPr-i 4 Å MS, toluene, –78°, 3-4 h O

OPr-i

OPr-i 4 Å MS, toluene, –78°, 3-4 h O

OPr-i

B[(–)-Ipc]2

n-C6H13

n-C6H13

n-C6H13

n-C6H13

n-C6H13

(86), 64, >99:1 d.r.

(52), >95:5 d.r.

(82)

(82)

>98:2

—

d.r.

(71), 93:7 d.r. SiMe2Ph

Ph

SiMe2Ph

(95), 81, >99:1 d.r.

SiMe2(OCy)

Cy

OH

OH

OH

OH

OH

OH

680

751

781

40

38, 40

45

472

C8

C7

NC

BPSO

OBn

OMe OH

H

H

O H

OMOM

O

TBDMSO

t-Bu

t-Bu

O

O

O H

H

Carbonyl Substrate

B

O

B

O O

B[(–)-Ipc]2

O

B[(–)-Ipc]2

SiMe2Ph

Ph

OMOM

PhMe2Si

TMS

OPh

B(OBu-n)2

Allylborane Reagent

FB(OBu-n)2

O

O

octane, 120°

Pt(C2H4)(PPh3)2,

,

Ph

PhMe2Si B

THF, –78°

THF, –78°, 4 h

Neat, rt, 4 d

OPh

–

,

Conditions

NC

BPSO

I

OPh OH

+

OBn

OH

SiMe2Ph

(48), 89:11 d.r.

OH

(80), 99:1 d.r.

OMOM

OH

SiMe2Ph

Ph

(75)

OMe OH

(77), >90, 9:1 d.r.

TMS

OMOM

OH

II OPh I + II (73), I:II = 37.3:1

t-Bu

TBDMSO

t-Bu

t-Bu

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

781

335

734, 788

521

46

Refs.

473

H

O H

R = MeO2C, Me, NC

R = CF3, NC

n-C7H15

R

O

Ph2N

Ph2N

Ph

PhMe2Si

Ph

MeO2C B

B

B[(+)-Ipc]2

B[(–)-Ipc]2

O

O

O

O

,

O O

O

,

,

3h

THF, –78° to 0°,

3h

THF, –78° to 0°,

80°, 5 h

I Pd2(dba)3, EtOAc,

Ph

PhMe2Si B

BF3, toluene, rt

+

Ph2N

+

(47), >95, >95:5 d.r.

n-C7H15

OH

(46), >95, >95:5 d.r.

Ph2N

OH

>99:1 d.r.

Ph

20 h

(81)

(84)

n-C7H15

(25)

NPh2

NPh2

(85)

(70)

(93)

(24)

H

OH

H

OH

NC

Me

MeO2C

R

n-C7H15

SiMe2Ph

24 h

NC

OH

Time

CF3

Ph

CO2Me

R

n-C7H15

R

R

OH

730

730

761

785

474

C8

n-C7H15

O

O

H

H

Carbonyl Substrate

Cl

Cl

Cl

TMS

O O

B[(+)-Ipc]2

O 2

OEt

OEt

O

B[(–)-Ipc]2

BBN

B

O

B

O

Allylborane Reagent

, benzene, rt

2

OEt O

Pt(dba)2, PCy3,

O

OEt

3. DBU

2. 8-HQ

6h

1. Ether, –95° to rt,

3. DBU

2. 8-HQ

6h

1. Ether, –95° to rt,

6h

Ether, –95° to 0°,

3. NaOH, H2O2

2. Aldehyde, –78°, 3 h

1.

O B

O

Ether, rt, 1-3 d

Conditions

H

H

n-C7H15

n-C7H15

O

(—), 88

(—), 95

O H

H

O +

+

(57), 97:3 d.r.

(—), 90

O

Cl

(68), 70, >19:1 d.r.

(79)

(—), 77

HO

TMS

OH

OH

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

790

790

789

185

32

Refs.

475

Ph

O

H

H

H

O

O

H

H

Cl

Cl

Cl

Cl

Cl

BBN

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

Cl,

LDA, THF, –78°

MeOBBN,

3. Aldehyde

2. BF3•OEt2

1.

3. DBU

2. 8-HQ

6h

1. Ether, –95° to rt,

3. DBU

2. 8-HQ

6h

1. Ether, –95° to rt,

3. DBU

2. 8-HQ

6h

1. Ether, –95° to rt,

3. DBU

2. 8-HQ

6h

1. Ether, –95° to rt,

I

III

OH

Cl

OH

O

O

O

O

Cl

+ Ph II

(—), >97

(—), 90

(—), 97

(—), 96

Cl

OH

I + II + III (86), II:(I+III) = 87:13

+ Ph

Ph

H

H

H

H

159

790

790

790

790

476

C9

C8

n-C8H17

O

Ph

O

O

H

H

O H

Carbonyl Substrate

Cl

Cl

Ph

PhMe2Si

Cl

O

B[(–)-Ipc]2

B[(–)-Ipc]2

B

O

B[(–)-Ipc]2

Allylborane Reagent Cl,

Cl,

3. Aldehyde

2. BF3•OEt2 (x equiv)

LDA, ether, –78°

MeOB[(–)-Ipc]2,

Cl,

3. Aldehyde

1.

,

,

LiNCy2, ether, –78°

MeOB[(–)-Ipc]2,

80°, 5 h

2. BF3•OEt2

1.

,

O O

I Pd2(dba)3, EtOAc,

Ph

PhMe2Si B

3. Aldehyde

O

LiNCy2, ether, –78°

MeOB[(–)-Ipc]2, 2. BF3•OEt2

1.

Conditions

I

x 1.33

2.5

OH

Ph

(—), 92

(70), 98, 99:1 d.r.

(60), >99:1 d.r.

SiMe2Ph

(85), 90, 99:1 d.r.

(—), 93

I Cl

OH

Cl

OH

n-C8H17

O

Ph

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

159

159, 762

761

159, 762

Refs.

477

Ph

Ph

H

H

Co2(CO)6

O

O

OMe

OR

OMe

O O

B

N

Ph

B[(+)-Ipc]2

B[(–)-Ipc]2

O 2

OEt

OEt

Ts

N

B[(–)-Ipc]2

B

O

Ts Ph

,

O

benzene, rt

2

OEt

Pt(dba)2, PCy3,

O

OEt

THF, –78° to rt, 15 h

THF, –78° to rt, 15 h

THF, –78°

3. Me2Zn, H2O

2. Aldehyde, –78°, 3 h

1.

O B

O

CH2Cl2, –78°

OH

OMe (75), >98, >97.5:2.5 d.r.

Ph

OH

>97.5:2.5

(62), >96 MOM

(CO)6Co2

>97.5:2.5

(75), >98 Me

d.r.

(5-10), 65

(60)

OR

OH

OMe

OH

O B

(78), 98

Ph R

(CO)6Co2

Ph

n-C8H17

n-C8H17

OH

747

747

747

185

791

478

C9

Ph

Ph

H

O H

Co2(CO)6

O

Carbonyl Substrate

THPO

OTHP

Cl

OMEM

MeO

B

O O

B

O

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

O

B[(–)-Ipc]2

Allylborane Reagent

Cl,

LiNCy2, ether, –78°

MeOB[(–)-Ipc]2,

Cl

THPO O B

O

Li,

O – B O OTHP, Cl

–100°

Ether, pentane,

3. Aldehyde

2. BF3•OEt2

1.

Ether, –78°, 5 h

15 h

THF, –78° to rt,

Conditions

Ph

Ph

Ph

Ph

Ph

OMe

II

I OTHP OH

OH

OH

Cl

OH

OMEM

OH

OH

OTHP

>97.5:2.5 d.r.

(50), >95,

OTHP

+

(90), 87

(85), 98, 98:2 d.r.

(76), 94, >99:1 d.r.

(62), 13:1 d.r.

I + II (76), I:II = 5.9:1

Ph

Ph

(CO)6Co2

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

52

46

505

159

292

747

Refs.

479 Bu-n

n-Bu

n-Bu

n-Bu

B O

B

O

O

O

O

B

O

B

O

O

O

OPr-i

O

OPr-i

OPr-i

O

OPr-i

OPr-i

OPr-i

O

O

O

OPr-i

OPr-i

B(OPr-i)2

B(OPr-i)2

R = TBDMS

Bu-n

RO

O

O

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

–78°, 5 h

4 Å MS, toluene,

18 h

THF, –78° to rt,

18 h

THF, –78° to rt,

–78°, 5 h

4 Å MS, toluene,

n-Bu

OH

OH

I

TBDMSO

Bu-n

Ph

Ph

OH

OH

Bu-n

Bu-n

I (98), 71, 98:2 d.r.

Ph

Ph

Ph

OH

(100), 62, 96:4 d.r.

(93), 70, 96:4 d.r.

(96), 95:5 d.r.

(95), 90:10 d.r.

(98), 73

740

740

740

772

772

88

480

C9

O2N

Ph

O H

O H

Carbonyl Substrate

Et

EtO2C

Bu-n

O B

O

O B

O

O

O

O 2

OEt

OEt

O

OPr-i

OPr-i

B(OPr-i)2

B

O

O

Allylborane Reagent

,

O

benzene, rt

2

OEt

Pt(dba)2, PCy3,

O

OEt

rt, 16-24 h

Sc(OTf)3, toluene,

3. NaOH, H2O2

2. Aldehyde, –78°, 3 h

1.

O B

O

CH2Cl2, rt, 5 h

–78°, 5 h

4 Å MS, toluene,

Conditions

O2N

Ph

Ph

Ph

O

Et

O

(59), 40, >19:1 d.r.

(95)

(100), 68, 96:4 d.r.

(—), 2.8:1 d.r.

OH

OH

OH

n-Bu

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

26

185

744

740

Refs.

481

Ph

O H

Ph

Ph

Ph

O

O

O

O

Ph

B

O

B

O

B

O

PhMe2Si

"

B

O B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

rt, 24 h

Ether, –78°, 2 h;

Ether, –78°, 2 h

Ether, –78°, 2 h

rt, 24 h

Ether, –78°, 2 h;

rt, 24 h

Ether, –78°, 2 h;

THF, –78°, 4 h

Ph

Ph

Ph

Ph

Ph

Ph SiMe2Ph OH

OH

OH

Ph

B

B

Ph

O

O

OH

Ph

(—)

(—)

(72), 91, >14:1 d.r.

Ph

O

OH

O

OH

(42), 95, >20:1 d.r.

OH

Ph

(76), 95

(40), 93, >20:1 d.r.

OH

OH

Ph

Ph

175

175

175

175

175

734

482

C9

Ph

Ph

O H

O H

Carbonyl Substrate

TMS

Et

EtO2C

PhMe2Si

OMOM

B

O

B

O

O

O

B

O

O

O

B

O

O

O

O

OPr-i

OPr-i

–78° to 0°, 1 h

4 Å MS, toluene,

Conditions

Neat, rt, 4 d

L.A., rt, 24 h

OPr-i 4 Å MS, toluene, –78° O

OPr-i

Allylborane Reagent

Ph

Ph

Ph

Ph

(62)

toluene CH2Cl2 CH2Cl2 CH2Cl2

Yb(OTf)3 Sc(OTf)3 Cu(OTf)2 Yb(OTf)3

TMS

(66)

toluene

OH

(63)

toluene Cu(OTf)2

(—), 90:10 d.r.

(38)

(52)

(64)

Solvent Sc(OTf)3

Et

O

SiMe2Ph

(75), 75

(70), 90

L.A.

O

OH

OMOM

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

521

26, 24

743

792

Refs.

483

C10

8

O H

O

O

H

H

O TrocO

n-C9H19

Ph

O

O

AcO

OMe

O H

EtO2C

Et

EtO2C

OMEM

TMS

TMS

O

O

O

B

O

B

O

"

O Ph

O

B[(–)-Ipc]2

B

O

B

O

O

OEt

OEt

24 h

L.A., toluene, rt,

2. pTSA

1. Neat, rt, 14 d

Toluene, rt, >12 d

Ether, –78°, 5 h

–78°

4 Å MS, toluene,

Ether, rt, 1-3 d TMS

(31), 13 (37), 21

Yb(OTf)3

(53), 3

(—), 60

(68), 18:1 d.r.

(78), 93, >99:1 d.r.

Cu(OTf)2

Sc(OTf)3

O

Et

O

OMEM

OH

O

I

OMe TMS

OH

(92)

(89), >98:2 d.r.

O

L.A.

n-C9H19

I

8

OH

O TrocO

n-C9H19

Ph

O

O

AcO

26

59, 26

59

292

193

32

484

C10

n-C9H19

O H

Carbonyl Substrate

R

O

B

O

B

O

O

B

O O Ph

B

O O Ph

B

O O

R = (–)-8-(2-naphthyl)menthyl

RO2C

R = (–)-8-phenylmenthyl

RO2C

R = (–)-8-phenylmenthyl

RO2C

R = (–)-8-phenylmenthyl

RO2C

EtO2C

Allylborane Reagent

2. pTSA, 3 h

1. Toluene, rt, 14 d

2. pTSA

1. Neat, rt, 14 d

2. pTSA

1. Neat, rt, 14 d

24 h

L.A., toluene, rt,

Toluene

Conditions

n-C9H19

n-C9H19

n-C9H19

n-C9H19

O

O

O

O

O

O

O

110°

Et

O

60-80°

Me

R Temp

R

n-C9H19

O

O

(30), 31

Yb(OTf)3

(—), 82

(75), 98

(—), 10

(93), 71

(29), –10

(68)

(40)

Cu(OTf)2

Sc(OTf)3

L.A.

16-24 h

16-120 h

Time

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

26

59, 26

59, 26

26

26

Refs.

485

C12

C11

OR

OPMB

O

OMe

OMe

H

R = TBDMS

PMBO

RO

O

AcO

OR

O H

O

H

O O

Ph

OMe

Bu-n

EtO2C

Ph

Me

H

Ph Ph

Et

B

O O

B(OPr-i)2

B[(+)-Ipc]2

B

O B[(+)-Ipc]2

B–Et2SePh

,

2h

THF, –78° to –20°,

rt, 24 h

Sc(OTf)3, toluene,

TMSCl

–78° to rt

CH2Cl2, MeOH,

12 h

2. Et3B, –78° to rt,

30 min

LDA, THF, –78°,

1. PhSe

OPMB

O

PMBO

RO

n-C9H19

OR

OMe

Bu-n

O

OH

(89.5), 76:13.5 d.r.

OMe

OH

(44)

(40)

AcO

O

B

OH

(83), 61:39 d.r.

(63), 10:1 d.r.

Et

OMe

O

OR

OH

O

794, 795

26

793

202

692

486

C13

BnO

MeO

MeO

MeO

n-C12H25

H

H

O H

OMe

O

O

O CH(OMe)2

OMe

OMe

O

OBn O

Carbonyl Substrate

H PhMe2Si

OMOM

MeO2C

OMEM

B[(+)-Ipc]2

O

O OPr-i

B

O

OPr-i 4 Å MS, toluene, –78° O

–78° to –20°, 23 h

Ether, THF,

BF3•SiO2, rt, 3 d

"

rt, 3 d

90°, 3 d

O

Sc(OTf)3 (10 mol%),

Ether, –90°

Conditions

"

B

O

B[(+)-Ipc]2

Allylborane Reagent

BnO

I (15)

I (19)

MeO

MeO

MeO

n-C12H25

O

I

(80)

O

OBn OH

SiMe2Ph

(96), >97.5:2.5 d.r.

(12)

(81), 95, >98:2 d.r.

CO2Me

OMOM

OH

OMe

OH CH(OMe)2

OMe

OMe

OMEM

OH

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

788

468

797

797

797

796

Refs.

487

C18

C17

MeO

MeO

OBn OBn

O

TBDPSO

OBn

Ph

O

O

O

O

OMe

O

O AcHN OBn

H

OTBDMS

H

H

OMe

OMOM

OMOM

OMOM

B[(+)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(+)-Ipc]2

—

16 h

THF, –78° to 10°,

–78° to rt, 3 h

Ether, THF,

THF, –78°

MeO

MeO

OBn OBn

O

TBDPSO

TBDPSO

Ph

OBn

O

O O

(78), 99:1 d.r.

(70), 10:1 d.r.

OMe

OMe

OH

(56), 6:1 d.r.

(77)

AcHN OTBDMS OBn

OMOM OH

OMOM

OH

OMOM

OH

798

469

452, 453

452, 453

488

C25

C20

H

2

R1

O

O

B

O

B

O

B

The starting material was prepared using different conditions.

H

O

OMOM

TMS

TMS

TMS

O

The reaction mixture was free of Mg2+ ions.

H

H

O

OR2 O

OR

2

b

H O H O

= MOM

H O H

R2

OR1

OR1

O

O

O

O

O 1. Toluene, 0°, 1 h

Conditions

1. Toluene, 0°, 1 h

rt, 1 h

2. KOBu-t, THF,

1. CH2Cl2, rt, 1 h

OPr-i 2. KH, THF, 0°, 10 min O

OPr-i

OPr-i 2. KH, THF, 0°, 10 min O

OPr-i

Allylborane Reagent

I

I

TMSO

H

(83), 15:1 Z:E

H O H

H O H

(70), >20:1 Z:E

OR1

(80), >20:1 Z:E

OR1

H

O

O

OR1

OR1

H

O

O

OMOM

OR2

OR2

Product(s) and Yield(s) (%), % ee

TABLE 6. ADDITION OF γ-SUBSTITUTED REAGENTS (Continued)

a

O

= TIPS,

OR1

R = TIPS, R = MOM

1

TMSO

I

I

OR

1

Carbonyl Substrate

801

800

799

Refs.

489

C2

C1

H

O

O

H

H

Carbonyl Substrate

n-Pr

Ph

R2

B(R1)2

B(Bu-n)2

Bu-n

B(Bu-n)2

BOMe(Thex)

C6H13-n

B(C6H13-n)2

C6H13-n

R1

Allylborane Reagent

n-BuLi, THF

O

n-BuLi, THF

O

O n-BuLi, THF

OMe,

OMe,

n-BuLi, THF

O

3. BCl3, –78° to rt

2. B(Bu-n)3, –78°

1.

Ether, 0°

3. BCl3, –78° to rt

–78°

OMe,

2. (n-C6H13)BOMe(Thex),

1.

Ph

3. BCl3, –78° to rt

2. B(C6H13-n)3, –78°

1.

3. BCl3, –78° to rt

OMe,

Conditions

2. BR13, –78°

1.

R2

HO

OH

HO

HO

HO

Pr-n

Ph

R2

(89)

Ph

Bu-n

(65)

(60), 56:44 d.r.

C6H13-n

(65)

(71)

(84)

Ph

(68)

(45)

n-Bu

Ph

Me

R2

n-C6H13

Ph

C6H13-n

R

1

n-Bu

R1

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS

802

803

802

802

802

Refs.

490

C3

C2

CCl3

O

O

O

H

H

H

Carbonyl Substrate

B

B(C5H9-c)2

B(C5H9-c)2

B(Bu-n)2

B

TMS

B[(–)-Ipc]2

B[(–)-Ipc]2

TMS

C5H9-c

c-C5H9

n-Pr

TMS

TMS

R

Allylborane Reagent

Cl ,

Cl ,

1.5 h

2. Aldehyde, –78° to rt,

–90° to rt

B(C5H9-c)3, THF,

1. Li

1.5 h

2. Aldehyde, –78° to rt,

B(C5H9-c)3, THF, –90°

1. Li

Ether, –78°, 3 h

Ether, 0°

THF, –78°, 3 h

Ether, –100°, 3 h

Ether, –100°, 2 h

Conditions

CCl3

OH

C5H9-c

OH

OH

Pr-n

TMS

TMS

(68), 89

(84)

C5H9-c

(75)

(74), 87

(74), 94

(72)

(71), 94

(72), 87

n-Pr

Me

R

Product(s) and Yield(s) (%), % ee

OH

OH

OH

R

OH

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

807

807

144

803

806

805

804

Refs.

491

Et

O H

Pr-n

R

n-Pr

R

R

B(Bu-n)2

B(OBu-n)2

B(OBu-n)2

BR2

BR2

BBN

Cl ,

Cl ,

Ether

Ether

1.5 h

2. Aldehyde, –78° to rt,

–90° to rt

BR3, THF,

1. Li

Ether, 0°

1.5 h

2. Aldehyde, –78° to rt,

BR3, THF, –90°

1. Li

Ether, rt, 15 min

Et

Et

Et

Et

Et

Et

Pr-n

OH

OH

Pr-n

R

OH

OH

OH

OH

(70)

R

n-Pr

Et

R

n-C6H13

(85)

(89)

(78)

(60)

(73)

(80)

(77)

n-C6H13

c-C5H9

R

c-C5H9

Cy

R

(70)

R

(82)

810

810

807

803

807

808, 809

492

C3

Et

O

O H

Carbonyl Substrate

TMS

Ph

Ph

Ph

BBN

B(C6H13-n)2

C6H13-n

Cl

B(Thex)

C6H13-n

B(OBu-n)2

B(OBu-n)2

Allylborane Reagent

Cl , C6H13-n

O n-BuLi, THF

Ph OMe,

THF, rt, 1.5 h

3. BCl3, –78° to rt

2. B(C6H13-n)3, –78°

1.

1.5 h

2. Aldehyde, –78° to rt,

THF, –90°

(Thex)B Cl ,

1. Li

Ether

Ether

Conditions

HO

HO

Et

Et

Et

OH

OH

OH

TMS

Ph

Ph

Ph

(86)

(62)

C6H13-n

(50)

C6H13-n

(52)

(76)

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

811

802

807

810

810

Refs.

493

C4

EtO

MeO

O

O

O

O

O

O

H

H

TMS

TMS

B[(–)-Ipc]2

B(C5H9-c)2

C5H9-c

BBN

BBN

TMS

BBN

TMS

B(OBu-n)2

BBN

Pr-n

,

Cl ,

Ether, –100°, 3 h

1.5 h

2. Aldehyde, –78° to rt,

B(C5H9-c)3, THF, –90°

1. Li

THF, 0°, 4 h

Sc(OTf)3 (7.5 mol%),

O

Ether, –78°, 3 h

Ether, 3 h

Ether

THF, rt, 1.5 h

EtO

MeO

HO

I

HO

O

O

HO Pr-n

OH

OH

OH

TMS

OH

OH

TMS 0º

–78°

Temp

83:17

85:15

d.r.

TMS

(68), 87

(84)

(90), 75:25 d.r.

C5H9-c

(62)

TMS

(95)

(55)

II TMS I + II (71), I:II = 91:9

+

Pr-n

805

807

812

598

598

810

811

494

C4

n-Pr

O H

O H

Carbonyl Substrate

TMS

TMS

Ts

Et

c-C5H9

B

TMS

N

B

N

Ph

Ts Ph

B(OBu-n)2

B

TMS

BBN

B(C5H9-c)2

Allylborane Reagent Cl ,

Ether, –78°, 3 h

CH2Cl2, –78°, 2-5 h

Ether

THF, –78°, 3 h

THF, rt, 1.5 h

1.5 h

2. Aldehyde, –78° to rt,

–90° to rt

B(C5H9-c)3, THF,

1. Li

Conditions

n-Pr

OH

OH

OH

OH

OH

TMS

TMS

C5H9-c

OH

(75-80), 97-98

(82), 94

Et

(30)

(87), 97

(79)

(84)

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

144

153

810

806

811

807

Refs.

495

i-Pr

O H

TMS

n-Pr

B

TMS

B

TMS

TMS B

B[(–)-Ipc]2

B(Bu-n)2

Ether, –100°, 3 h

Ether, 0°

Ether, –78°, 3 h

Ether, rt, 15 min

Ether

"

BBN

—

B(OBu-n)2

TMS

THF, –78°, 3 h

Ether, –78°, 3 h

i-Pr

i-Pr

i-Pr

i-Pr

n-Pr

n-Pr

n-Pr

n-Pr

TMS

OH

OH

OH

OH

TMS

Pr-n

OH

OB(OBu-n)2

OH

OH

(76), 99

(78)

(81), 93

(88)

(60)

(50-60)

(87), 98

(80), 93

805

803

144

808, 809

810

2

806

144

496

C4

i-Pr

O H

Carbonyl Substrate

TMS

Ts

B

TMS

TMS

c-C5H9

R

N

B

Ph

Ts N Ph

BBN

Pr-n

TMS

BBN

B(C5H9-c)2

B[(–)-Ipc]2

Allylborane Reagent

Cl ,

CH2Cl2, –78°, 2.5 h

THF, rt, 1.5 h

THF, –78°, 3 h

THF, rt, 1.5 h

1.5 h

2. Aldehyde, –78° to rt,

–90° to rt

B(C5H9-c)3, THF,

1. Li

Ether, –100°, 2 h

Conditions

i-Pr

I

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

OH

OH

OH

OH

+

Pr-n i-Pr

OH

(77), 97

(82)

Pr-n

(70), 96

Ph

(78)

(80), 96

(72), 96

n-Pr

Me

R

(76), 94

II TMS I + II (74), I:II = 88:12

TMS

TMS

C5H9-c

OH

R

OH

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

TMS

153

811

806

811

807

804

Refs.

497

C5

t-Bu

i-Pr

O

O

O

H

O H

TMS

O

O OCH(Pr-i)2

O

OCH(Pr-i)2

B[(–)-Ipc]2

B(C5H9-c)2

C5H9-c

B

TMS

BBN

x equiv

O

B

BBN

BBN

Cl ,

Ether, –100°, 3 h

1.5 h

2. Aldehyde, –78° to rt,

B(C5H9-c)3, THF, –90°

1. Li

Ether, –78°, 3 h

Ether, rt

Toluene, –78°, 20 h

Ether, rt, <5 min

Ether, rt, <5 min

t-Bu

t-Bu

t-Bu

t-Bu

i-Pr

OH

OH

OH

OH

TMS

OH

OH

OH

x 3.0

1.5

(75), 92

C5H9-c

(75), 94

90 min

15 min

Time

(89)

(71)

(86)

(88)

(89)

(74), 99

(78), 99

805

807

144

808, 809

813

809

809

498

C5

t-Bu

O H

Carbonyl Substrate

Ts

B

TMS

TMS

c-C5H9

N

B

O

B

N

Ph

Ts

O

O OPr-i

O

Ph

OPr-i

B(OBu-n)2

TMS

BBN

B(C5H9-c)2

Allylborane Reagent Cl ,

CH2Cl2, –78°, 2.5 h

Toluene, –78°

Ether, 40°, 48 h

THF, –78°, 3 h

THF, rt, 1.5 h

1.5 h

2. Aldehyde, –78° to rt,

–90° to rt

B(C5H9-c)3, THF,

1. Li

Conditions

OH

OH

t-Bu

t-Bu

OH

TMS

TMS

C5H9-c

OH

HO

t-Bu

t-Bu

t-Bu

t-Bu

OH

(74), 98

(47), 93

(50)

(80), 98

(85)

(79)

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

153

123

814

806

811

807

Refs.

499

Et

O

O Et

TMS

TMS

Ts

Ph

OEt

OEt

O

BBN

B(OBu-i)2

BBN

Pr-n

BBN

Ph

Ts N

O

O

BBN

N

B

O

B

DMSO, 150°, 2 h

THF, rt, 1.5 h

THF, rt, 1.5 h

Ether, rt, <5 min

Ether, rt

CH2Cl2, –78°, 2.5 h

Toluene, –78°, 46 h

Et

Et

Et

Et

Et

Et

Et

Et

I

t-Bu

t-Bu

OH

OH

OH

OH

Pr-n +

(91)

Et

Et

II

OH

Pr-n

(87)

(87)

(88)

1h 15 min

Time

(78), >99

(53), 88

(60)

I + II (75), I:II = 83:17

TMS

TMS

OH

OH

HO

TMS

814

811

811

809

808, 809

812

153

123

500

C6

C5

O

O

n-C5H11

n-Pr

HO

EtO

O

O

H

O

H

H

O

O H

Carbonyl Substrate

TMS

R

TMS

O

B

O

B

O

O

O

O

BBN

BBN

OR

OR

O

OEt

OEt

O

B(Bu-n)2

Bu-n

BBN

Allylborane Reagent

O n-BuLi, THF

R O ,

THF, rt, 1.5 h

Toluene, –78° to rt

Toluene, –78°, 46 h

Ether, rt, 15 min

3. BCl3, –78° to rt

2. B(Bu-n)3, –78°

1.

THF, rt, 2 h

Conditions

O

O

(55)

Ph

OH

TMS

HO

(82)

Pr-i

Et

R

(50), 70

(79)

60:40

d.r. 60:40

(65)

Me

R

OH

TMS

(39), —

(39-66), 62-66

Bu-n

(90)

R

HO

OH

HO

O

n-C5H11

n-Pr

HO

EtO

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

811

123

123

808, 809

802

815

Refs.

501

x equiv

TMS

Ts

Ts

Et

Ts

N

B

N

B

N

B

O

B

O

B

Ph

Ph

N

Ph

Ts

N

Ts

N

Ts

O

O

O

O

Ph

Ph

Ph

OR

OR

O

OCH(Pr-i)2

OCH(Pr-i)2

O

BBN

Pr-n

CH2Cl2, –78°, 2.5 h

CH2Cl2, –78°, 2.5 h

CH2Cl2, –78°, 2.5 h

Toluene

Toluene, –78°, 20 h

THF, rt, 1.5 h

n-C5H11

n-C5H11

n-C5H11

I

n-C5H11

R

OH

OH

OH

(63), >95

(75-80), 97-98

(82), >99

Et

(72), 97

(81), 94

(75), 88

(81), 91

–78º

Pr-i

Temp –78° to –20°

Et

I

5.0

1.5

x

I:II = 88:12

OH

I + II (78), Pr-n

TMS

+

II

OH

TMS

Pr-n

n-C5H11

I

n-C5H11

OH

153, 816

153

153

123

813

811

502

C7

C6

Ph

t-Bu

O H

O

O

Carbonyl Substrate

TMS

TMS

"

BBN

BBN

BBN

B(OBu-n)2

BBN

Pr-n

BBN

Allylborane Reagent

Ether, rt, 15 min

Ether, rt, 1 h

Ether, 40°, 12 h

THF, rt, 1.5 h

THF, rt, 1.5 h

Ether, rt, 15 min

Ether, rt, 1 h

Conditions

Ph

t-Bu

OH

I (88)

OH

OH

Pr-n

OH

TMS

OH

TMS

OH

OH

TMS

(88)

(68)

II

(82)

I

Pr-n +

(91)

(94)

I:II = 91:9

I + II (76),

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

808, 809

812

814

811

811

808, 809

812

Refs.

503 TMS

R

B

TMS

B[(–)-Ipc]2

B(C5H9-c)2

BBN

B(Bu-n)2

B(C5H9-c)2

C5H9-c

c-C5H9

TMS

n-Pr

TMS B

Cl ,

Cl ,

THF, –78°, 3 h

Ether, –100°

1.5 h

2. Aldehyde, –78° to rt,

–90° to rt

B(C5H9-c)3, THF,

1. Li

THF, rt, 1.5 h

Ether, 0°

1.5 h

2. Aldehyde, –78° to rt,

–90°

B(C5H9-c)3, THF,

1. Li

Ether, –78°, 3 h

Ph

Ph

Ph

Ph

Ph

Ph

Ph

TMS

Pr-n

OH

TMS

R

OH

C5H9-c

OH

OH

OH

OH

OH

(60), 98

TMS

n-Pr

R

(85)

(88)

(79)

C5H9-c

(78), 93

3h

2h

Time

(86)

(74), 89

(77), 87

806

805

804

807

811

803

807

144

504

C7

Ph

O H

Carbonyl Substrate

O

B

O

Ts

N

B

O

B

N

Ph

Ts

O

O

Ph

OEt

OEt

O

R = CH(Pr-i)2, C10H21-n

"

OR

O

OR

B(OBu-n)2

O R = Et, Pr-i

TMS

BBN

Pr-n

Allylborane Reagent

CH2Cl2, –78°, 2.5 h

Toluene, –78°, 44 h

Toluene, –78°, 20 h

Toluene

Ether, 40°, 3 h

THF, rt, 1.5 h

Conditions

Pr-n + Ph

OH

I

OH

C10H21-n

CH(Pr-i)2

44 h

21 h

Time

(70), 63

(<50), 79

(<50), 73

–78°

Pr-i R

Temp –78° to –20°

Et

(72)

I R

OH

HO

(43), 79

(52), 60

II Pr-n I TMS I + II (72), I:II = 87:13

I (76), 96

Ph

I

Ph

Ph

Ph

OH

TMS

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

153

123

813

123

814

811

Refs.

505

R

H

R = O2N, MeO

R = H, MeO, O2N

O

H

Ts

O

B

O

N

O

O

Ph

Ts

O

B

O

B O

BBN

N

B

H

OEt

OEt

O

Ph

O

O

,

,

Toluene, –78° to –20°, 20 h

Ether, rt, 1 h

CH2Cl2, –78°, 2.5 h

Pd(PPh3)4

HB

CDCl3, –78°

R

R

Ph

Ph

Ph

OH

OH

OH

OH

OH

(58), 72 (66), 72

O2N MeO

R

(94)

(99)

MeO O2N

(96)

H

R

(72), >99

(57)

(43), 34, 3.4:1.4 d.r.

123

812

153

550

817

506

C7

Cy

O H

Carbonyl Substrate

O

B

O

B

x equiv

TMS

c-C5H9

O

O

O

O

OEt

OEt

O

OEt

OEt

O

B[(–)-Ipc]2

B(C5H9-c)2

B(C5H9-c)2

C5H9-c

BBN

Allylborane Reagent

Cl ,

Cl ,

Toluene, –78°, 44 h

Toluene, –78° to rt, 20 h

Ether, –100°, 3 h

1.5 h

2. Aldehyde, –78° to rt,

–90° to rt

B(C5H9-c)3, THF,

1. Li

1.5 h

2. Aldehyde, –78° to rt,

–90°

B(C5H9-c)3, THF,

1. Li

Ether, rt, 1 h

Conditions

Cy

Cy

Cy

Cy

Cy

Cy

OH

OH

OH

TMS

C5H9-c

OH

OH

OH

(74), 87

1.5

1.0

x

(78), 96

(86)

C5H9-c

(91)

(56), 92

(85), 86

(88)

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

123

123

805

807

807

812

Refs.

507

O

O

O

O

B

x equiv

O

B

O

B

O

B

O

O

O

O

O

O

O

O

x equiv O

O

B

O

B

OCH(Pr-i)2

OCH(Pr-i)2

O

OCH(Pr-i)2

OCH(Pr-i)2

O

O(menthyl)

O(menthyl)

O

OR

OR

O

OPr-i

OPr-i

O

OPr-i

OPr-i

O

Toluene, –78°, 20 h

Toluene, –78°, 20 h

Toluene, –78°, 20 h

Toluene, –78°, 20 h

Toluene, –78°, 22 h

Toluene, –78°, 24 h

Cy

Cy

Cy

Cy

Cy

Cy

OH

OH

OH

OH

OH

OH

(82), 99

3.0

1.0

x

(69), 92

(89), 99

(88), 98

(85), 98

(37), 93 c-C10H19

(42), 91 menthyl

(88), 92

(81), 91

(81), 95

(70), 91

c-C5H9

i-Pr

Et

R

1.5

1.0

x

(42), 90

813

813

813

813

123

123

508

C8

C7

Ph

Cy

O

O H

Carbonyl Substrate

TMS

TMS

Et

Ts

Ts Ph

Ph

BBN

BBN

Pr-n

BBN

N

Ts

Ph

Ph

N

Ph

B

N

Ts

N

Ts

N

B

N

B

Ts

Ph

Allylborane Reagent

THF, rt, 1.5 h

THF, rt, 1.5 h

Ether, rt

CH2Cl2, –78°, 2.5 h

CH2Cl2, –78°, 2.5 h

CH2Cl2, –78°, 2.5 h

Conditions

Ph

Ph

Ph

Cy

Cy

Cy

Et

Ph

(93)

TMS

+

1h

15 min

Time

(78), 95

(78), >99

(82), 92

Pr-n

II Pr-n

I TMS OH

OH

TMS

OH

OH

OH

OH

OH

I:II = 54:46

I + II (88),

(97)

(86)

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

811

811

812

808, 809

153

153

153

Refs.

509

C9

Ph

n-Bu

O

O

O

O

H

O

H

H

TMS

Ts

N

B

O

B

N Ph

OEt

OEt

O

BBN

Ph

Ts

O

O

BBN

BBN

B(OBu-n)2

,

O ,

Toluene, –78°, 2.5 h

Toluene, –78° to 0°, 20 h

THF, –78° to –10°, 1.5 h

THF, 0°, 4 h

Sc(OTf)3 (7.5 mol%),

n-Bu

THF, 0°, 4 h

Sc(OTf)3 (7.5 mol%),

O

Ether, 40°, 95 h

Ph

Ph

n-Bu

Ph

O

OH

OH

OH

OH

TMS

OH

OH

(44)

(79), 98

(67), 79

(65)

(71)

(76)

153

123

815

812

812

814

510

C10

C9

Ph

Ph

R

O

O

O H

OMe

H

R = H, NO2

R = H, OMe, NO2

H

O

H

O

O

O

Carbonyl Substrate

TMS

TMS

Ts

N

BBN

BBN

BBN

N

B Ph

BBN

BBN

Ph

Ts

Allylborane Reagent

,

O ,

O ,

THF, 20°, 4 h

BF3•OEt2 (15 mol%),

R

THF, 0°, 4 h

Sc(OTf)3 (7.5 mol%),

R

Ether, rt, 1 h

THF, rt, 2 h

THF, –78° to –15°, 1.5 h

Toluene, –78°, 2.5 h

Conditions

I

Ph

Ph

NO2

H

R

R

(22)

O

OH

TMS

(73)

I

OH

TMS OH

OH O

OH

(99)

OMe

(86)

(98)

(77) OMe NO2

(73) H

R

(82)

(74), >99

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

812

812

812

815

815

153

Refs.

511

Ph

Ph

O

Br

O

O

O

O

O

OMe

H

H

H

H

TMS

x equiv

"

O

B

O

B

O

B

O

O

O

O

O

O

BBN

BBN

OEt

OEt

O

OCH(Pr-i)2

OCH(Pr-i)2

O

OCH(Pr-i)2

OCH(Pr-i)2

O

O ,

,

2. BF3•OEt2

1. THF, rt, 2 h

Toluene, –78°, 22 h

Toluene, –78°, 20 h

Toluene, –78°, 20 h

THF, 20°, 4 h

Br BF3•OEt2 (15 mol%),

Ph

O

THF, 0°, 4 h

Br Sc(OTf)3 (7.5 mol%),

Ph

Ph

I (70)

Ph

O

OH

O

(90), 99

(82)

OH

(74), 92

OH

5.0

x

OH

1.5

TMS

I

Br

(67), 98

(52), >95

(83)

815

123

813

813

812

812

512

C16

C13

C11

Ph

Ph

Ph

Ph

Ph

O Ph

R

O

O

O

H

H

H

Carbonyl Substrate

"

BBN

BBN

BBN

BBN

Allylborane Reagent

O ,

O ,

THF, 0°, 4 h

Sc(OTf)3 (7.5 mol%),

Ph

Ph

Ether, rt, <5 min

THF, 0°, 4 h

Sc(OTf)3 (7.5 mol%),

Ph

R

THF, 20°, 4 h

BF3•OEt2 (15 mol%),

Ph

O ,

THF, 0°, 4 h

Sc(OTf)3 (7.5 mol%),

Ph

O ,

Conditions

Ph

Ph Ph

Ph

Ph

OH

OH

(90)

1:1 (70)

Me

(93)

1.2:1

d.r. (89)

(77)

CH2OBn

R

OH

I

OH

R

I (78)

Ph

Product(s) and Yield(s) (%), % ee

TABLE 7. ADDITION OF ALLENYL AND PROPARGYL REAGENTS (Continued)

812

809

812

812

812

Refs.

513

C2

C1

H

O

O

H

H

Carbonyl Substrate

O

N Ph

O

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B Ph

O

O B

B(Pr-n)2

B(Pr-n)2

THF, –78°

THF, –78°

THF, –78° to rt

Ether, –78° to rt

2. DDQ

1. 100°

–60° to 0°

–60° to 0°

Conditions

TABLE 8. ADDITION OF CYCLIC REAGENTS Allylborane Reagent

O

OH

OH

OH

O

(29), >95:5 d.r.

(24), 95, >99:1 d.r.

(36), 93, >99:1 d.r.

(66), 94, >99:1 d.r.

(94), >97.5:2.5 d.r.

Ph

OH

(91)

(50)

N

B Ph

O

OH

OH

Product(s) and Yield(s) (%), % ee

820

820

69, 820

819

818

545

545

Refs.

514

C2

H

O

CCl3

O

O

O

H

H

H

Carbonyl Substrate

B[(–)-Ipc]2

B Ph

B Ph

B(Pr-n)2

B(Pr-n)2

B(Pr-n)2

THF, –78°, 4 h

Ether, –78° to rt

Ether, –78° to rt

–60° to 0°

–60° to 0°

–70° to 0°

Conditions

OH

+ II

O

(81), >98, 98:2 d.r.

(95), >97.5:2.5 d.r.

(94), >97.5:2.5 d.r.

(74)

(70)

B Ph

OH

OH

O

B Ph

OH

OH

OH

Product(s) and Yield(s) (%), % ee

I + II (65-80), I:II = 53:47

CCl3

I

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

255

819

819

545

545

545

Refs.

515

C3

Cl

O

Cl

H

TBDMSO

O

O H

O

OEt

B Ph

B[(–)-Ipc]2

B Ph

B Ph

O

B

O

O

OEt, O 1 (1 mol%), 4 Å MS, neat

B

Cl

O

OH

O

B Ph

(41)

(82)

(94), >97.5:2.5 d.r.

B Ph

B Ph

O

OEt

(92), >97.5:2.5 d.r.

Cl

O

Ether, –78° to rt

Cl

O

H OH

(58), 92, >99:1 d.r.

1

Cr

TBDMSO

THF, –78° to rt

Ether, –78° to rt

Ether, –78° to rt

O

N

2. Aldehyde, 45°, 48 h

1.

O

819

820

819

819

150

516

C3

O

O

H

H

Carbonyl Substrate

Bn

O

N

N

B

O

N Ph

Bn

H

H

O

N O

S

+

O

–

B R1

R2

Ph

B[(–)-Ipc]2

O

O B

O

N N

B

Bn

O

O

O– S+ N

Ph ,

toluene, 80°, 70 h

Bn

O

—

THF, –78° to rt

2. DDQ

1. 40°

Conditions

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

(89)

Cy Cy

N H H OH N Bn Bn

O

S+ N

(62)

(72)

n-C6H13 Thex

Ph

(85)

Cy Thex

O–

(70)

H

I + II

R

Cy

HO

Thex

R2 +

I:II

54:46

54:46

97:3

98:2

II

R2

OH

(65), 93, >99:1 d.r.

Ph

(71), >95:5 d.r.

2

OH

N

O

R1

I

OH

OH

O

HO

Product(s) and Yield(s) (%), % ee

199

601

820

818

Refs.

517

"

B

O

O

Br

B

B

Me N

O

H

H

O

H

H

O

B

O

O

O

O

O

N Ph

O

CO2Me

N Me

CO2Me

80°

rt

CH2Cl2, –78° to 20°

60°, 12 h

Et3N, CH2Cl2

OH

OH

OH

Br

I (22)

OH I

O

O

O

O

(70)

N Ph

O

(8)

CO2Me

(40)

CO2Me

(66)

89

89

821

183

821

518

C3

O

O H

Carbonyl Substrate

"

O

N

B(Pr-n)2

B(Pr-n)2

BBN

B Ph

O

O B Ph

O

, HBBN, pentane, rt, 24 h

–60° to 0°

–70° to 0°

2. Ketone, rt, 2 h

1.

Pentane, rt, 2 h

Ether, –78° to rt

2. DDQ

1. 40°

Conditions

I

O

N

+

OH

(87)

OH

(61), >95:5 d.r.

II I + II (65-80), I:II = >100:1

OH

O

(88)

Ph

(86)

B Ph

O

HO

Product(s) and Yield(s) (%), % ee

OH

I (68)

I

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

545

545

103

103

819

818

Refs.

519

C4

n-Pr

O

O

H

O

O

H

B[(–)-Ipc]2

B(Pr-n)2

B(Pr-n)2

B R1

R2

B Ph

B Ph

THF, –78° to rt

–60° to 0°

–60° to 0°

—

Ether, –78° to rt

Ether, –78° to rt

n-Pr

OH

OH

OH

(69), 90, >99:1 d.r.

(69)

(75)

94:6 (84)

53:47

(85) n-C6H13

Thex

Cy

Thex

I:II

II

99:1

HO

R2

OH

(82) Cy

Thex

R2 +

(44)

(90)

I + II

R2

R1

I

OH

B Ph

B Ph

OH

O

O

820

545

545

601

819

819

520

C4

i-Pr

O H

Carbonyl Substrate

O

O

O

B

B

B

O

H

H

O

H

H

O

CO2Me

O

O

O

O

N Ph

O

B R1

R2

Benzene, 20°, 4 h

80°

rt

—

Conditions

i-Pr

i-Pr

i-Pr

i-Pr

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

OH

OH

OH

(75)

(67)

(76), 9:1 d.r.

CO2Me

O

O

O

O

N Ph

O

53:47

(81)

C5H9-c

Thex

I:II 97:3

(85)

Cy

Thex

R2 Pr-i

I + II

R2

R1

HO II

OH

R2 +

I

OH

OH

Product(s) and Yield(s) (%), % ee

822

89

89

601

Refs.

521

BnO

O H

B

"

B

B

O

O

O

x equiv

O

O

O

CO2Me

CO2Me

CO2Me 80°

O B

O CO2Me,

See table

Benzene, 20°, 4 h

Benzene, 20°, 4 h

2. Aldehyde, benzene, rt

1.

I

Pressure — 10 kbar — —

1.5 1.5 2 3

OH

OH

x

BnO

I (63), 9:1 d.r.

I (67), 9:1 d.r.

BnO

80°

80°

rt

80°

Temp

16 h

16 h

24 h

15 h

Time

CO2Me

(50)

(38)

(22)

(29)

(69), 9:1 d.r.

CO2Me

183, 821

821, 822

824

823

522

C4

MeO2C

BnO

O

O

H

H

Carbonyl Substrate

B

O B

O

i-PrO2C

O

O

B CO2Me

CO2Me

O

CO2Pr-i

CO2Me

OBn

O

80°

O B

O CO2Me,

CO2Pr-i

Benzene, 20°, 4 h

2. Aldehyde, benzene, rt

1.

i-PrO2C

80°, 15.5 h

Conditions

O

BnO

BnO

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

O

OH

OH

(67), 9:1 d.r.

CO2Me

(49), 70

CO2Me

OBn

(33)

CO2Me

Product(s) and Yield(s) (%), % ee

822

823

183, 821

Refs.

523

C5

i-Pr

n-Bu

O

O

O

H

O

H

H

O

O

O

B

O

B

B(Pr-n)2

B(Pr-n)2

OEt

O

OEt

B[(–)-Ipc]2

O

O

OEt, O 1a (1 mol%), 4 Å MS, neat

B

O

OEt, O 1a (1 mol%), 4 Å MS, neat

B

2. Aldehyde, 45°, 24 h

1.

O

THF, –78° to rt

–60° to 0°

–70° to 0°

2. Aldehyde, 45°, 48 h

1.

O

+

O

II

i-Pr

H OH

OH

O

OH

OEt (81)

(67), 90, >99:1 d.r.

(91)

OH

OEt (61)

I + II (65-80), I:II = >100:1

n-Bu

I

OH

H OH

150

820

545

545

150

524

C5

t-Bu

i-Pr

O H

O H

Carbonyl Substrate

O

B

O

O

O

N Ph

O

N Ph

O

B Ph

B Ph

O

NMe2

N

B

TESO

O

O O

N Ph, N NMe2 O

B

B

O

N Ph,

O

Ether, –78° to rt

Ether, –78° to rt

O toluene, 80°, 24 h

TESO

O

toluene, 80°, 72 h

O

Conditions

t-Bu

t-Bu

i-Pr

i-Pr

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

O

O

B Ph

B Ph

OTES OH

H OH NMe2

N

(88)

(50)

(94), >97.5:2.5 d.r.

(95), >97.5:2.5 d.r.

O

N Ph

O

O

N Ph

O

Product(s) and Yield(s) (%), % ee

819

819

825

181

Refs.

525

C6

O

O

EtO2C

O H

O H

O

O

B(Pr-n)2

B Ph

B(Pr-n)2

–70° to 0°

Ether, –78° to rt

–60° to 0°

Ether, –78° to rt

2. Aldehyde, 110°, 48 h

20°, 5 h

R

OEt

O

O OEt, 1a (3 mol%), BaO, neat,

B

R

B Ph

O

B

1. O

I

O

(40)

B Ph

II I + II (65-80), I:II = 9:1

+

99:1

—

d.r.

OH

(96), >97.5:2.5 d.r.

B Ph (92)

OH

O

O

OH

O

(76), 95

OEt

CH2CH=C(Me)2

O

(74), —

H OH

C7H15-n

R

EtO2C

R

545

819

545

819

198

526

C7

Ph

O H

Carbonyl Substrate

B Ph

B(Pr-n)2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B[(–)-Ipc]2

B Ph

Ether, –78° to rt

–70° to 0°

THF, –78°

THF, –78°

THF, –78°

THF, –78° to rt

Ether, –78° to rt

Conditions

Ph

I

Ph

Ph

O

OH

+ II

O

B Ph

(94), >97.5:2.5 d.r.

Ph

OH

(40), 79, 24:1 d.r.

(28), 93, >99:1 d.r.

(38), 95, >99:1 d.r.

(71), 94, >99:1 d.r.

(97), >97.5:2.5 d.r.

I + II (65-80), I:II = 3:2

Ph

OH

B Ph

Product(s) and Yield(s) (%), % ee

OH

OH

HO

Ph

Ph

Ph

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

819

545

826

820

820

820

819

Refs.

527 O

O

R1

O

O

R2

O

H

O

H NMe2

N

B

NMe2

N

B

N

N

B

B

O

O

S+ N R

O–

O

N Me

O

O

N Ph

O

O

O

O

,

B

O

2

O

N Ph,

O

,

B

O O

B

O O– S+ N R,

N NMe2 O toluene, 80°, 70 h

O

N Me, N NMe2 O toluene, 80°, 72 h

O

R R toluene, 80°, 72 h

N 1N

O

Rh4(CO)12

HB

Ph

Ph

Ph

Ph

N Ph

O

(92)

H H OH NMe2

N

H

H OH NMe2

N

O

S+ N R

O–

O

N Me

O

N H OH 1 N 2 O R R

OH

(52) (69) Bu-t

Ac

Ph

Ph

R2

Pr-n

R

(50)

H

Me

H

R1

(42)

(46)

199

181

(46) 181

550

528

C7

Ph

O H

Carbonyl Substrate

H

O

B

O

R R

O

O

H NMe2

N

B

MeO

O O

N

N

B

O

S+ N

–

O

O

N Ph

O

Ph

O O– S+ N

N NMe2 O

B Ph ,

N N

B

O

O

—

N Ph,

O

toluene, 80°, 72 h

MeO

R R

O

toluene, 80°, 70 h

O

Conditions

Ph

Ph

Ph

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

O–

R

9:1 (55)

Me

(90), >100:1

>97.5:2.5

d.r. (55)

OMe

R O

H

OH

Ph

N Ph

O

O

S+ N

R

H OH N

N

H H OH NMe2

N

H (65)

Product(s) and Yield(s) (%), % ee

52

181, 182

182

199

Refs.

529

R

"

R = H, O2N, MeO

B

O

H

O

R = H, MeO, Cl, F

O

B

H

H

O

O

O

B OMe

O

O

Y

O

OEt

O

O B

O

O

O

OEt, O 1a (1 mol%), 4 Å MS, neat

B

2. Aldehyde, 25-45°, 24 h

1.

O

Neat, 70°

2. NaOH, H2O2, THF

1. Ether, 0°, 20 h

2. DDQ

1. 40°

See table

I

R

Ph

Ph

O

(82) (92) (81) MeO

H OH

O

O

OH

O

Ph

O2N

I

O

HO

H

R

OH

OH

Y

O

rt

(69)

(80)

OEt

F

Cl

827

818

89

(80), 96

(77), 93

150

(85), 95 151 MeO (84), 96

H

R

(90), 3:1 d.r.

(59), >95:5 d.r.

80°

NPh

Temp

O

Y

530

C7

R1 = H, Br

H

R1 = H, O2N, MeO

R1

O

Carbonyl Substrate

O

R2

O

R3

O

O

N Y

O

O

NMe2

N

B

O

N Ph

O

Y = C6H4CO2-p

N

N

B

N N

B

O

N Y

O

O N Ph,

O

N NMe2 O

B

toluene, 80°, 72 h

O

O R2 R3 toluene, 80°, 72 h

O

Conditions

R1

R1

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

(47) (48) (52)

H O2N MeO

H OH NMe2

H

Me

H

N

Me

Me

Br

R3 Me

Me

R2

H

R1

R1

H OH N R2 R3

N

O

N Ph

O

(60)

(54)

(62)

O

N Y

O

Product(s) and Yield(s) (%), % ee

181

182

Refs.

531

O 2N

R

O H

R1 = see table

O H

TESO

O B

O

B

O

O B

TESO

O

O

O

O

R2

O

N

Ph

O

N

O

N

O

O

B

O N R2,

O

B

O

O N

toluene, 110°, 18 h

TESO

O

2. DDQ

1. 40°

O O,

O toluene, 80-100°, 16-24 h

TESO

O

O2N

R1

Ph Ph Me Me Me

MeO Br O2N MeO Br

O

R

O

(78)

(67)

(89)

(93)

(82)

(92)

(76)

O

(67)

N

O

p-Cl

p-NO2

O

(56)

(48)

m-NO2 (77)

o-NO2

R

OTES OH (71), 4:1 d.r.

>95:5 d.r.

O

Ph

Ph

O2N

N

Ph

H

HO

R2

R1

OTES OH

N R2

O

825

818

825

532

C7

Cl

NO2

O H

O H

Carbonyl Substrate

O

O B

O

O B

O

O B

CO2Et

CN

O

N

CO2Et

CN

Ph

O

2. DDQ

1. 40°

2. DDQ

1. 40°

2. DDQ

1. 40°

Conditions

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

N Ph

O

CN

CO2Et (30), >95:5 d.r.

CO2Et

HO

(52), >95:5 d.r.

CN

HO

(83), >95:5 d.r.

O

HO

Cl

NO2

NO2

Product(s) and Yield(s) (%), % ee

818

818

818

Refs.

533

R1

R2 O H

R3

O

O

N

N

B

O

B

R4

O

O

O

N R5

O

OEt

O

N N

B

O N R5,

O

O R3 R4 toluene, 80°, 72 h

O

2. Reflux, 12 h

O

B

OEt, CH2Cl2, rt, 24 h

1. O

(81) (95) (80)

H H H O2N

Cl F O2N H

R3 Me Me Me Me H H H Me Me H H

R2 H H H H H H H H MeO H H

H H O2N MeO H H H H H H H

Me Me Ph Ph Ph Me

p-CF3C6H4 p-MeOC6H4 Ph Ph Ac Boc

Ph

Ph

Me

Ph

R5

Ph

O

N R5

O

Ph

Me

Me

Me

Me

R4

H OH N R 3 R4

(66)

H

R2

(70)

H

MeO

N

(77)

R2

OEt

H

O

R1

R2

H OH

R1

R1

R1

(61)

(42)

(68)

(65)

(55)

(77)

(76)

(48)

(52)

(50)

(75)

182

828

534

C7

Cy

O

O H

O

Carbonyl Substrate

O

O

O

O

N Me

O

OEt

B Ph

B(Pr-n)2

NMe2

N

B

O

B

O

O

B

O O

Ether, –78° to rt

–70° to 0°

N Me, N NMe2 O toluene, 80°, 72 h

O

2. Reflux, 12 h

O

B

OEt, CH2Cl2, rt, 24 h

1. O

Conditions

Cy

Cy

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

N

O

I

+

(45)

O

II

N Me

O

OEt

OH

(39)

O

B Ph (53)

I + II (65-80), I:II = 98:2

OH

H OH NMe2

H OH

Product(s) and Yield(s) (%), % ee

819

545

182

828

Refs.

535

C8

Ph

O

O

H

H

O H

O

O

O

"

O

B

O

NMe2

N

B

OEt

O

N Me

O

B Ph

B Ph

O N Me,

O

N NMe2 O

B

O

Neat, 70°

2. Reflux, 12 h

O

B

OEt, CH2Cl2, rt, 24 h

1. O

toluene, 80°, 72 h

O

Ether, –78° to rt

Ether, –78° to rt

O

B Ph

H OH

I

O

(95)

N Me O

OEt

H OH NMe2

N

O

(94), >97.5:2.5 d.r.

I (82), 96

Ph

B Ph

(97), >97.5:2.5 d.r.

O

(50)

151

828

182

819

819

536

C9

C8

Ph

O 2N

Ph H

O

OTBDPS

O

H

O H

Carbonyl Substrate

O

O

O

"

O

B

O

B

"

O

B

O

O

O

OEt

OEt

OEt

O

B

O

OEt,

O

B

O

OEt,

Neat, 70°

2. Reflux, 12 h

CH2Cl2, rt, 24 h

1. O

2. Aldehyde, 40°, 24 h

1a (1 mol%), 4 Å MS, neat

1. O

70°

Neat, 70°

Conditions

10 h

O H OH I

48 h

neat

Time

toluene

Solvent

I (87), 96

Ph

O2N

I

Ph O H I OH

OEt

H OH

(65)

(78)

OEt

(92)

O

OEt

(82), 96

Product(s) and Yield(s) (%), % ee

TBDPSO

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

(81)

151

828

150

829

151

Refs.

537

C11

C10

n-C10H21

O

O

O

H

O H OTBDPS

O

O

B

O

O

B

TMS

O

O

OEt

OEt

BBN

B(Pr-n)2

SPh

O

O

B

O

OEt,

2. Aldehyde, 45°, 24 h

1a (1 mol%), 4 Å MS, neat

1. O

2. NaOH, 4 h

1. THF, 0° to rt, 5.5 h

–70° to 0°

Neat, 70°

OH

H OH

+

O

II

OEt

O

H OH

O

O

OEt

(89)

OTBDPS

SPh (73)

OH

(87), 96

I + II (65-80), I:II = >100:1

n-C10H21

I

Ph

150

830

545

151

538

C14

a

Ph

O

B Ph

B Ph

Ether, –78° to rt

Ether, –78° to rt

Conditions

Ph

Ph

Ph

Ph

TABLE 8. ADDITION OF CYCLIC REAGENTS (Continued) Allylborane Reagent

The structure for catalyst 1 appears on the third page of Table 8.

Ph

Carbonyl Substrate

O

O

B Ph

B Ph

(94)

(90)

Product(s) and Yield(s) (%), % ee

819

819

Refs.

539

C7

H

H

H

H

O

O

O

O

O

OBn

O

B

O

B

O

O

B

Carbonyl Substrate

B

O

O

O

O

OMe

OMe

OMe

OBn

O

B O

Yb(OTf)3, H2O, 90°, 2 h

MeO

OMe

HCl, H2O, THF, 1 d

MeO

TFA, H2O, THF, 1 d

MeO

HCl, H2O, THF, 1 d

MeO

B O

O

B O

O B

O

O

Conditions

O

,

,

,

,

TABLE 9. INTRAMOLECULAR ADDITIONS

O

BnO

H

H

H

H

OH

H

OH

OH

H

H

H

OH

(28) (18)

DMF

(58) THF

CH2Cl2

Solvent

(66), 53:47 d.r.

(55)

(48)

Product(s) and Yield(s) (%), % ee

173

82

82

82

Refs.

540

C7

H

H

O

O

O

O

B

O O

B

O O

Carbonyl Substrate

O

O B

OMe O

O B O

O

Me

O

O

O B

O

O B O

Yb(OTf)3, H2O, CH3CN, 90°, 2 h

MeO

OMe

rt, 30 min

O N Li O

Me

Yb(OTf)3, H2O, CH3CN, rt, 12 h

MeO

MeO L.A., H2O, CH3CN, 90°, 2 h

OMe

Conditions

,

,

,

, I

O H

H

H

OH

OH

— >96:4

(58) (77)

Er(OTf)3 Yb(OTf)3

H2O (pH 7)

pH 7 buffer, THF

(70-74)

(60)

—

(55)

Conditions

—

(42)

—

—

d.r.

Sm(OTf)3

(44)

(56)

AgOTf

CuOTf

LiBF4

L.A.

Product(s) and Yield(s) (%), % ee

I (61), >93.5:6.5 d.r.

I

O

H

I (66)

TABLE 9. INTRAMOLECULAR ADDITIONS (Continued)

173

832

831

177

173

Refs.

541

H

H

H

H

O

O

O

O

R

N

B

O B

N

Ac N

B

O

O

B

N

Cbz

O

R

O

O

O

O

R N

O

O B

O B

O

O B O

,

CH3CN, rt, 1 d

L.A., H2O

MeO

OMe

Ac N O B

H2/CO (5 kbar), THF, 65°, 5 d

Rh(CO)2acac, BIPHEPHOS,

Cbz N

H2/CO (5 kbar), 60°, 4 d

Rh(CO)2acac, BIPHEPHOS,

MeO

OMe

MeO acetal cleavage

OMe

O

O

,

,

,

H

H

R

N

H

Yb(OTf)3

LiBF4

I

OH

L.A.

H Cbz

N

R

N

CO2Me

Boc

R

CH2Cl2

CH3CN

Solvent

(66)

Cbz

Ts

R

(49)

(51)

(45)

(43)

(66)

(80)

(60)

LiBF4, 2% H2O/CH3CN, rt

OH

(56)

DMSO, dioxane, H2O, 100°

O

(30)

(21)

SnCl2 • 2H2O, CH2Cl2, rt

dppe, Pd(OTf)2, acetone, rt

Acetal Cleavage

H

H OH

I

I

172

178

178

179

832

542

C8

C7

H

H

H

H

H

O

O

O

O

O

O

O

Cl

B

O

O

B

B

O

B

O

O

O

O

B

O

O

O

Carbonyl Substrate

acetal cleavage

MeO

OMe

acetal cleavage

MeO

OMe

HCl, H2O, THF, 1 d

MeO

OMe

CH3CN, rt, 1 d

CH3CN, rt, 1 d

Cl

O B

B O

O B

O

O

Conditions

O

,

,

,

H

H

TABLE 9. INTRAMOLECULAR ADDITIONS (Continued)

H

O

H

H

H

H

OH

OH

OH

H

H

Cl

82

172

(9) (74)

LiBF4, H2O, CH3CN

(51)

(51) 80

(55)

TMSOTf, acetone

SnCl2 • 2H2O, CH2Cl2

TFA, H2O, CHCl3, 0°

Acetal Cleavage

TFA, H2O, CHCl3, 0°

Refs.

172

dppe, Pt(OTf)2, acetone (17) 80

Acetal Cleavage

(17), 20:80 E:Z

(72)

(70), 94:6 d.r.

Product(s) and Yield(s) (%), % ee

H

OH

O

OH

543

H

H

H

H

H

O

O

O

O

O

OBn

OBn

OBn

OBn

OBn

B

O

B

O

B

O

O

B

O

O

B

O

O

O

O

OBn

O

OBn O B O

O B O

O B

OMe OBn

O

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

O B

O OBn TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

OBn TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

O B

,

,

,

,

,

BnO

BnO

BnO

BnO

BnO

H

H

H

H

H

H

H

H

H

H

OH

OH

OH

OH

OH

(54), >99:1 d.r.

(75), 51:49 d.r.

(57), 53:47 d.r.

(46), 70:30 d.r.

(35), >99:1 d.r.

171

171

171

171

171

544

C8

H

H

H

H

H

O

O

O

O

O

2

2

OBn

B

O

O

B

N

O

O

B

O

B

Ts

O

O

O

B

O

O

O

O

Carbonyl Substrate O B O

OMe 2

O

O B O

2

O

O B O

Ts N O B O

,

,

,

,

B O

O

Br,

,

Pd(OAc)2, PPh3 (3 equiv)a

I

O

60°, 4 d

Rh(CO)2acac, BIPHEPHOS, H2, CO, 5 kbar,

MeO

OMe

Yb(OTf)3, H2O, CH3CN, 90°, 2 h

MeO

OMe

Yb(OTf)3, H2O, CH3CN, 90°, 2 h

MeO

H

OMe OBn

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

Conditions

O

O

BnO

TABLE 9. INTRAMOLECULAR ADDITIONS (Continued)

N

Ts

H

H

O

OH

OH

OH

H

H

H

H (58), 51:49 d.r.

(47)

(83), 97:3 d.r.

(66), >90.5:9.5 d.r.

(56), >98.5:1.5 d.r.

OH

OH

Product(s) and Yield(s) (%), % ee

174

179

173

173

171

Refs.

545

C9

H

H

H

H

H

O

O

O

O

O O B O

O

B

B

O

B

O

O

O

B

O

O

B

O

O

O

O ,

O B O

O

O B O

O B

O

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

O B

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

2. NaOH, H2O2

THF, 60°, 24 h

B2(catechol)2, (Ph3P)2Pt(C2H4),

1. H

,

,

,

,

HO

H

H

H

H

H

H

H

H

H

OH

OH

OH

OH

OH

(42), >99:1 d.r.

(65), 93:7 d.r.

(46), >99:1 d.r.

(66), 85:15 d.r.

(10), >19:1 d.r.

833

833

833

833

186

546

C9

H

H

O

CO2Et

O

O

O

O

B

O

B O

O

O

B

O O

B

O O

Carbonyl Substrate O B O

O B O

B O O

B B O

O

OAc,

,

toluene, 100°

Pd(dba)2, AsPh3 (2 equiv)a,

CO2Et

O

O

O

pH 7 buffer, THF, rt, 30 min

O

Me N O Me O Li,

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

TFA, CHCl3/H2O (4:1), 0°, 3 h

MeO

OMe

Conditions

,

,

HO

TABLE 9. INTRAMOLECULAR ADDITIONS (Continued)

CO2Et

O

H

H

H

H

OH

OH

OH

(62)

(35)

(47), >99:1 d.r.

(44), 95:5 d.r.

Product(s) and Yield(s) (%), % ee

180

834

833

833

Refs.

547

C10

H

O

H

H O

TBDMSO

O

O

B

O

O

B

O

O

B

O

O

O

O

B O

O

,

B O O

O Me O Li,

Me N

H

O N Me

O Me

O Li,

O

pH 7 buffer, THF, rt, 30 min

O

H

O B

pH 7 buffer, THF, rt, 16 h

TBDMSO O

THF, 60°, 24 h

B2(catechol)2, (Ph3P)2Pt(C2H4),

H

2. NaOH, H2O2

1.

O

O

H

H

O

H

H

OH

TBDMSO

OH

OH

O

(51)

OH

(56), >19:1 d.r.

(38)

831

834

186

548

C10

O

O

I

O OMe,

O B O

CO2Et

O B O

O

2

CO2Et

O

OAc,

O

O

O

Br,

,

Pd(OAc)2 , PPh3 (3 equiv)a

CO2Et

B

toluene, 100°

Pd(dba)2, AsPh3 (2 equiv)a,

O B

LiBF4, H2O, CH3CN, rt, 1 d

H

O

O

O

B

H

H

O

O

Conditions

O

I (71)

I

H

H

EtO2C

TABLE 9. INTRAMOLECULAR ADDITIONS (Continued)

H MeO

H

Carbonyl Substrate

OH

O

H

H

OH

(82)

(76)

Product(s) and Yield(s) (%), % ee

174

180

177

Refs.

549

O

O

C(O)Me

Me(O)C

Me(O)C

O

O

B

O

B

O

O

B

O

O

O

O

O

O

Br,

,

O B O

OAc,

O

2

C(O)Me

O

OAc,

toluene, 100°

Pd(dba)2, AsPh3 (2 equiv)a,

O

O B

toluene, 100°

Pd(dba)2, AsPh3 (2 equiv)a,

2

O Pd(OAc)2, dppf, PPh3 (3 equiv)a

B

Me(O)C Me(O)C

I

COMe

HO

O

O

HO

HO

O

(52)

(71)

(50)

180

180

174

550

C10

H

H

H

O

O

O

O

B

O

B

O

B

O

O

O

B

O

B

O

B

O

O

O

O

Carbonyl Substrate O

,

O

,

O

,

2. NaOH, H2O2

THF, 60°, 24 h

B2(catechol)2, (Ph3P)2Pt(C2H4),

1. H

2. NaOH, H2O2

THF, 60°, 24 h

B2(catechol)2, (Ph3P)2Pt(C2H4),

1. H

2. NaOH, H2O2

THF, 60°, 24 h

B2(catechol)2, (Ph3P)2Pt(C2H4),

1. H

Conditions

TABLE 9. INTRAMOLECULAR ADDITIONS (Continued)

OH

OH

OH

OH

OH

OH (64), >19:1 dr

(57), >19:1 d.r.

(44), >19:1 d.r.

Product(s) and Yield(s) (%), % ee

186

186

186

Refs.

551

C11

O

H

O

O

H

H

H O

B

O

O

O

O

H

O B O

O

O

O

O B O

,

O B

O B

O H Br Pd(OAc)2, PPh3 (3 equiv)a

I

,

, O Br H dioxane/THF (3:1), Pd(PPh3)4, 70°, 3 h

, IZn

H2/CO, 65°, 3 d

H Rh(CO)2acac, BIPHEPHOS,

O

H

B O

H2/CO (5 kbar), 65°, 3 d

O

O B

, O Rh(CO)2acac, BIPHEPHOS,

O

H

I (78)

HO

O

I

O

H

H

H

O

O

H

(67)

H

H

O

H

O

H

H

H

H

H

O

O

H

OH

I

+

II

I + II (52), I:II = 1:1

II

+

I + II (48), I:II = 1:1

O

I

O

OH

174

79

177

177

552

C11

O

CO2Et

O

CO2Me

O

O

B

O

B

O

B

O

O

O

O

Carbonyl Substrate

I

O

B B O

O

OAc,

,

O O

,

Br,

O

CO2Et

O

2

,

OAc,

a

toluene, 100°

Pd(dba)2, AsPh3 (2 equiv)a,

O B

Pd(OAc)2, PPh3 (3 equiv)

CO2Me

O B

toluene, 100°

O Pd(dba)2, AsPh3 (2 equiv)a,

O

O

Conditions

TABLE 9. INTRAMOLECULAR ADDITIONS (Continued)

O

CO2Et

OH

CO2Me

OH

OH

(72)

(71)

(77)

Product(s) and Yield(s) (%), % ee

180

174

180

Refs.

553

C13

C12

O

H

H O

H

H

CO2Et

O

CO2Et

O

O

O

B

O

O

B

B

O

O

O

O

I

O

,

CO2Et

O

2

OAc,

,

CO2Et

O

O

H

O

H

H

O

Br,

B O

O

Me N O Me O Li,

equiv)a

pH 7 buffer, THF, rt, 30 min

O

H

Pd(OAc)2 , PPh3 (3

O B

toluene, 100°

Pd(dba)2, AsPh3 (2 equiv)a,

O B

O

H

H

O

H

H

CO2Et

OH

O

H

H

(64)

OH

(71)

(46)

831

174

180

554

C13

a

H

O

B O

Equivalents are relative to catalyst.

O

Carbonyl Substrate

O

Br

, I

O B O

Pd(OAc)2, PPh3 (3 equiv)a

H

Conditions

,

TABLE 9. INTRAMOLECULAR ADDITIONS (Continued)

OH (80)

Product(s) and Yield(s) (%), % ee

174

Refs.

ALLYLBORATION OF CARBONYL COMPOUNDS

555

REFERENCES 1

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64 65 66 67 68 69 70 71 72 73

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90 91

92 93 94

ORGANIC REACTIONS

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Hancock, K. G.; Kramer, J. D. J. Am. Chem. Soc. 1973, 95, 6463. Hancock, K. G.; Kramer, J. D. J. Organomet. Chem. 1974, 64, C29. 97 Le Serre, S.; Guillemin, J. C. Organometallics 1997, 16, 5844. 98 Batey, R. A.; Thadani, A. N.; Smil, D. V. Tetrahedron Lett. 1999, 40, 4289. 99 Batey, R. A.; Thadani, A. N.; Smil, D. V.; Lough, A. J. Synthesis 2000, 990. 100 Thadani, A. N.; Batey, R. A. Org. Lett. 2002, 4, 3827. 101 Lautens, M.; Maddess, M. L.; Sauer, E. L. O.; Ouellet, S. G. Org. Lett. 2002, 4, 83. 102 Hoffmann, R. W.; Sander, T. Chem. Ber. 1990, 123, 145. 103 Kramer, G. W.; Brown, H. C. J. Org. Chem. 1977, 42, 2292. 104 Metternich, R.; Hoffmann, R. W. Tetrahedron Lett. 1984, 25, 4095. 105 Wang, Z.; Meng, X.-J.; Kabalka, G. W. Tetrahedron Lett. 1991, 32, 4619. 106 Wang, Z.; Meng, X.-J.; Kabalka, G. W. Tetrahedron Lett. 1991, 32, 5677. 107 Pace, R. D.; Kabalka, G. W. J. Org. Chem. 1995, 60, 4838. 108 Kabalka, G. W.; Yang, K.; Wang, Z. Synth. Commun. 2001, 31, 511. 109 Wang, Z.; Meng, X. J.; Kabalka, G. W. Tetrahedron Lett. 1991, 32, 1945. 110 Kabalka, G. W.; Narayana, C.; Reddy, N. K. Tetrahedron Lett. 1996, 37, 2181. 111 Buynak, J. D.; Geng, B.; Uang, S.; Strickland, J. B. Tetrahedron Lett. 1994, 35, 985. 112 Cherest, M.; Felkin, H.; Prudent, N. Tetrahedron Lett. 1968, 9, 2199. 113 Roush, W. R. J. Org. Chem. 1991, 56, 4151. 114 Hoffmann, R. W.; Zeiss, H.-J.; Ladner, W.; Tabche, S. Chem. Ber. 1982, 115, 2357. 115 Hoffmann, R. W.; Weidmann, U. Chem. Ber. 1985, 118, 3966. 116 Anh, N. T.; Eisenstein, O. Nouv. J. Chim. 1977, 1, 61. 117 Cornforth, J. W.; Cornforth, R. H.; Mathew, K. K. J. Chem. Soc. 1959, 112. 118 Roush, W. R.; Adam, M. A.; Walts, A. E.; Harris, D. J. J. Am. Chem. Soc. 1986, 108, 3422. 119 Gung, B. W.; Xue, X. W. Tetrahedron: Asymmetry 2001, 12, 2955. 120 Hoffmann, R. W.; Herold, T. Angew. Chem., Int. Ed. Engl. 1978, 18, 768. 121 Herold, T.; Schrott, U.; Hoffmann, R. W.; Schnelle, G.; Ladner, W.; Steinbach, K. Chem. Ber. 1981, 114, 359. 122 Hoffmann, R. W.; Herold, T. Chem. Ber. 1981, 114, 375. 123 Haruta, R.; Ishiguro, M.; Ikeda, N.; Yamamoto, H. J. Am. Chem. Soc. 1982, 104, 7667. 124 Roush, W. R.; Walts, A. E.; Hoong, L. K. J. Am. Chem. Soc. 1985, 107, 8186. 125 Roush, W. R.; Hoong, L. K.; Palmer, M. A. J.; Park, J. C. J. Org. Chem. 1990, 55, 4109. 126 Roush, W. R.; Halterman, R. L. J. Am. Chem. Soc. 1986, 108, 294. 127 Gung, B. W.; Xue, X. W.; Roush, W. R. J. Am. Chem. Soc. 2002, 124, 10692. 128 Roush, W. R.; Park, J. C. J. Org. Chem. 1990, 55, 1143. 129 Roush, W. R.; Park, J. C. Tetrahedron Lett. 1990, 31, 4707. 130 Roush, W. R.; Park, J. C. Tetrahedron Lett. 1991, 32, 6285. 131 Roush, W. R.; Banfi, L. J. Am. Chem. Soc. 1988, 110, 3979. 132 Roush, W. R.; Grover, P. T. J. Org. Chem. 1995, 60, 3806. 133 Reetz, M. T.; Zierke, T. Chem. Ind. (London) 1988, 663. 134 Chen, Y.; Eltepu, L.; Wenthworth, J. P. Tetrahedron Lett. 2004, 45, 8285. 135 Wu, T. R.; Shen, L.; Chong, J. M. Org. Lett. 2004, 6, 2701. 136 Brown, H. C.; Jadhav, P. K. J. Am. Chem. Soc. 1983, 105, 2092. 136a Jadhav, P. K.; Bhat, K. S.; Perumal, P. T.; Brown, H. C. J. Org. Chem. 1986, 51, 432. 137 Brown, H. C.; Bhat, K. S. J. Am. Chem. Soc. 1986, 108, 5919. 138 Brown, H. C.; Jadhav, P. K. Tetrahedron Lett. 1984, 25, 1215. 139 Racherla, U. S.; Brown, H. C. J. Org. Chem. 1991, 56, 401. 140 Jadhav, P. K.; Bhat, K. S.; Perumal, P. T.; Brown, H. C. J. Org. Chem. 1986, 51, 432. 141 Short, R. P.; Masamune, S. J. Am. Chem. Soc. 1989, 111, 1892. 142 Garcia, J.; Kim, B. M.; Masamune, S. J. Org. Chem. 1987, 52, 4831. 143 Burgos, C. H.; Canales, E.; Matos, K.; Soderquist, J. A. J. Am. Chem. Soc. 2005, 127, 8044. 144 Lai, C.; Soderquist, J. A. Org. Lett. 2005, 7, 799. 145 Canales, E.; Prasad, K. G.; Soderquist, J. A. J. Am. Chem. Soc. 2005, 127, 11572. 146 Hoffmann, R. W.; Landmann, B. Chem. Ber. 1986, 119, 1039. 96

558 147 148 149 150 151 152

153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170

171 172 173

174 175 176

177 178 179 180 181 182

183 184 185 186 187 188

189 190 191 192 193 194

ORGANIC REACTIONS

Hoffmann, R. W.; Dresely, S. Tetrahedron Lett. 1987, 28, 5303. Hoffmann, R. W.; Weidmann, U. J. Organomet. Chem. 1980, 195, 137. Hoffmann, R. W.; Dresely, S.; Hildebrandt, B. Chem. Ber. 1988, 121, 2225. Gao, X.; Hall, D. G. J. Am. Chem. Soc. 2003, 125, 9308. Deligny, M.; Carreaux, F.; Toupet, L.; Carboni, B. Adv. Synth. Catal. 2003, 345, 1215. Gao, X.; Hall, D. G.; Deligny, M.; Favre, A.; Carreaux, F.; Carboni, C. Chem.—Eur. J. 2006, 13, 3132. Corey, E. J.; Yu, C.-M.; Lee, D.-H. J. Am. Chem. Soc. 1990, 112, 878. Tamao, K.; Nakajo, E.; Ito, Y. J. Org. Chem. 1987, 52, 957. Wuts, P. G. M.; Bigelow, S. S. J. Chem. Soc., Chem. Commun. 1984, 736. Coleman, R. S.; Kong, J.-S. J. Am. Chem. Soc. 1998, 120, 3538. Brown, H. C.; Narla, G. J. Org. Chem. 1995, 60, 4686. Hunt, J. A.; Roush, W. R. J. Org. Chem. 1997, 62, 1112. Hu, S.; Jayaraman, S.; Oehlschlager, A. C. J. Org. Chem. 1996, 61, 7513. Barrett, A. G. M.; Seefeld, M. A.; Williams, D. J. J. Chem. Soc., Chem. Commun. 1994, 1053. Chataigner, I.; Zammattio, F.; Lebreton, J.; Villi´eras, J. Synlett 1998, 275. Ishihara, K.; Kaneeda, M.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 11179. Rauniyar, V.; Hall, D. G. Angew. Chem., Int. Ed. 2006, 45, 2426. Wada, R.; Oisaki, K.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 8910. Masamune, S.; Choy, W.; Petersen, J. S.; Sita, L. R. Angew. Chem., Int. Ed. Engl. 1985, 24, 1. Brown, H. C.; Bhat, K. S.; Randad, R. S. J. Org. Chem. 1987, 52, 319. Brown, H. C.; Bhat, K. S.; Randad, R. S. J. Org. Chem. 1989, 54, 1570. Ogawa, A. K.; Armstrong, R. W. J. Am. Chem. Soc. 1998, 120, 12435. Roush, W. R.; Palkowitz, A. D.; Palmer, M. A. J. J. Org. Chem. 1987, 52, 316. Roush, W. R.; Hoong, L. K.; Palmer, M. A. J.; Straub, J. A.; Palkowitz, A. D. J. Org. Chem. 1990, 55, 4117. Sander, T.; Hoffmann, R. W. Liebigs Ann. Chem. 1993, 1193. Hoffmann, R. W.; Hense, A. Liebigs Ann. 1996, 1283. Yamamoto, Y.; Kurihara, K.; Yamada, A.; Takahashi, M.; Takahashi, Y.; Miyaura, N. Tetrahedron 2003, 59, 537. Watanabe, T.; Sakai, M.; Miyaura, N.; Suzuki, A. J. Chem. Soc., Chem. Commun. 1994, 467. Flamme, E. M.; Roush, W. R. J. Am. Chem. Soc. 2002, 124, 13644. Barrett, A. G. M.; Braddock, D. C.; de Koning, P. D.; White, A. J. P.; Williams, D. J. J. Org. Chem. 2000, 65, 375. Hoffmann, R. W.; Kr¨uger, J.; Bruckner, D. New J. Chem. 2001, 25, 102. Hoffmann, R. W.; Br¨uckner, D.; Gerusz, V. J. Heterocycles 2000, 52, 121. Hoffmann, R. W.; Br¨uckner, D. New J. Chem. 2001, 25, 369. Ahiko, T.-a.; Ishiyama, T.; Miyaura, N. Chem. Lett. 1997, 811. Tailor, J.; Hall, D. G. Org. Lett. 2000, 2, 3715. Tour´e, B. B.; Hoveyda, H. R.; Tailor, J.; Ulaczyk-Lesanko, A.; Hall, D. G. Chem. Eur. J. 2003, 9, 466. Six, Y.; Lallemand, J.-Y. Tetrahedron Lett. 1999, 40, 1295. Goldberg, S. D.; Grubbs, R. H. Angew. Chem., Int. Ed. 2002, 41, 807. Morgan, J. B.; Morken, J. P. Org. Lett. 2003, 5, 2573. Ballard, C. E.; Morken, J. P. Synthesis 2004, 1321. Woodward, A. R.; Burks, H. E.; Chan, L. M.; Morken, J. P. Org. Lett. 2005, 7, 5505. Nicolaou, K. C.; Ninkovic, S.; Sarabia, F.; Vourloumis, D.; He, Y.; Vallberg, H.; Finlay, M. R. V.; Yang, Z. J. Am. Chem. Soc. 1997, 119, 7974. Bratz, M.; Bullock, W. H.; Overman, L. E.; Takemoto, T. J. Am. Chem. Soc. 1995, 117, 5958. Roush, W. R.; Wada, C. K. J. Am. Chem. Soc. 1994, 116, 2151. Williams, D. R.; Plummer, S. V.; Patnaik, S. Angew. Chem., Int. Ed. 2003, 42, 3934. Denmark, S. E.; Yang, S.-M. J. Am. Chem. Soc. 2002, 124, 15196. Marron, T. G.; Roush, W. R. Tetrahedron Lett. 1995, 36, 1581. Roush, W. R.; Marron, T. G. Tetrahedron Lett. 1993, 34, 5421.

ALLYLBORATION OF CARBONYL COMPOUNDS 195

196

197 198 199 200 201 202 203 204 205

206 207 208 209 210 211 212 213 214 215

216 217

218 219 220 221 222

223 224 225 226 227 228 229 230 231 232 233 234 235

236 237 238

239

559

Scheidt, K. A.; Tasaka, A.; Bannister, T. D.; Wendt, M. D.; Roush, W. R. Angew. Chem., Int. Ed. 1999, 38, 1652. Smith, A. B., III; Adams, C. M.; Barbosa, S. A. L.; Degnan, A. P. J. Am. Chem. Soc. 2003, 125, 350. Andersen, M. W.; Hildebrandt, B.; Dahmann, G.; Hoffmann, R. W. Chem. Ber. 1991, 124, 2127. Gao, X.; Hall, D. G. J. Am. Chem. Soc. 2005, 127, 1628. Tour´e, B. B.; Hall, D. G. Angew. Chem., Int. Ed. 2004, 43, 2001. Tour´e, B. B.; Hall, D. G. J. Org. Chem. 2005, 69, 8429. Hicks, J. D.; Flamme, E. M.; Roush, W. R. Org. Lett. 2005, 7, 5509. Flamme, E. M.; Roush, W. R. Org. Lett. 2005, 7, 1411. Owen, R. M.; Roush, W. R. Org. Lett. 2005, 7, 3941. Ramachandran, P. V.; Reddy, M. V. R.; Brown, H. C. Tetrahedron Lett. 2000, 41, 583. Nelson, S. G.; Cheung, W. S.; Kassick, A. J.; Hilfiker, M. A. J. Am. Chem. Soc. 2002, 124, 13654. Lambert, W. T.; Roush, W. R. Org. Lett. 2005, 7, 5501. Hoffmann, R. W.; Sch¨afer, F.; Haeberlin, E.; Rohde, T.; K¨orber, K. Synthesis 2000, 2060. Hoffmann, R. W.; Rohde, T.; Haeberlin, E.; Sch¨afer, F. Org. Lett. 1999, 1, 1713. Denmark, S. E.; Fu, J. Chem. Rev. 2003, 103, 2763. Modern Aldol Reactions; Mahrwald, R., Ed.; Wiley-VCH: Weinheim, 2004. Cowden, C. J.; Paterson, I. Org. React. 1997, 51, 1. Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1. Konig, K.; Neuman, W. P. Tetrahedron Lett. 1967, 493. Keck, G. E.; Tarbet, K. H.; Geraci, L. S. J. Am. Chem. Soc. 1993, 115, 8467. Costa, A. L.; Piazza, M. G.; Tagliavini, E.; Trombini, C.; Umani-Ronchi, A. J. Am. Chem. Soc. 1993, 115, 7001. Faller, J. W.; Sams, D. W. T.; Liu, X. J. Am. Chem. Soc. 1996, 118, 1217. Kim, J. G.; Waltz, K. M.; Garcia, I. F.; Kwiatkowski, D.; Walsh, P. J. J. Am. Chem. Soc. 2004, 126, 12580. Yanagisawa, A.; Nakashima, H.; Ishiba, A.; Yamamoto, H. J. Am. Chem. Soc. 1996, 118, 4723. Yanagisawa, A.; Nakashima, H.; Ishiba, A.; Yamamoto, H. Synlett 1997, 88. Marshall, J. A. Chem. Rev. 1996, 96, 31. Furuta, K.; Mouri, M.; Yamamoto, H. Synlett 1991, 561. Ishihara, K.; Mouri, M.; Gao, Q.; Maruyama, T.; Furuta, K.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 11490. Gauthier, D. R.; Carreira, E. M. Angew. Chem., Int. Ed. Engl. 1996, 35, 2363. Bode, J. W.; Gauthier, D. R.; Carreira, E. M. Chem. Commun. 2001, 2560. Wadamoto, M.; Ozasa, N.; Yanagisawa, A.; Yamamoto, H. J. Org. Chem. 2003, 68, 5593. Yamasaki, S.; Fujii, K.; Wada, R.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2002, 124, 6536. Denmark, S. E.; Fu, J. J. Am. Chem. Soc. 2001, 123, 9488. Denmark, S. E.; Fu, J. Chem. Commun. 2003, 167. Masse, C. E.; Panek, J. S. Chem. Rev. 1995, 95, 1293. Kubota, K.; Leighton, J. L. Angew. Chem., Int. Ed. 2003, 42, 946. Hackman, B. M.; Lombardi, P. J.; Leighton, J. L. Org. Lett. 2004, 6, 4375. Duthaler, R. O.; Hafner, A. Chem. Rev. 1992, 92, 807. Xia, G.; Yamamoto, H. J. Am. Chem. Soc. 2006, 128, 2554. Arnauld, T.; Barrett, A. G. M.; Seifried, R. Tetrahedron Lett. 2001, 42, 7899. Cavallaro, C. L.; Herpin, T.; McGuiness, B. F.; Shimshock, Y. C.; Dolle, R. E. Tetrahedron Lett. 1999, 40, 2711. Micalizio, G. C.; Schreiber, S. L. Angew. Chem., Int. Ed. 2002, 41, 3272. Hoffmann, R. W.; Dresely, S. Synthesis 1988, 103. Mikhailov, B. M.; Bubnov, Y. N.; Tsyban, A. V.; Grigoryan, M. S. J. Organomet. Chem. 1978, 154, 131. Brown, H. C.; Jadhav, P. K. J. Org. Chem. 1984, 49, 4089.

560 240

241 242 243 244 245 246 247 248

249

250

251 252 253

254 255 256

257

258

259 260 261 262 263 264 265

266 267 268

269

270 271

272 273 274 275 276 277 278 279 280

ORGANIC REACTIONS

Brown, H. C.; Randad, R. S.; Bhat, K. S.; Zaidlewicz, M.; Racherla, U. S. J. Am. Chem. Soc. 1990, 112, 2389. Brown, H. C.; Kulkarni, S. V.; Racherla, U. S. J. Org. Chem. 1994, 59, 365. Brown, H. C.; Kulkarni, S. V.; Racherla, U. S.; Dhokte, U. P. J. Org. Chem. 1998, 63, 7030. Redlich, H.; Schneider, B.; Hoffmann, R. W.; Geueke, K. J. Liebigs Ann. Chem. 1983, 393. Herold, T.; Hoffmann, R. W. Angew. Chem., Int. Ed. Engl. 1978, 17, 768. Itsuno, S.; Watanabe, K.; El-Shehawy, A. A. Adv. Synth. Catal. 2001, 343, 89. Itsuno, S.; El-Shehawy, A. A.; Sarhan, A. A. React. Funct. Polym. 1998, 37, 283. Reddy, M. V. R.; Yucel, A. J.; Ramachandran, P. V. J. Org. Chem. 2001, 66, 2512. Kumar, D. J. S.; Madhavan, S.; Ramachandran, P. V.; Brown, H. C. Tetrahedron: Asymmetry 2000, 11, 4629. Ramachandran, P. V.; Padiya, K. J.; Rauniyar, V.; Reddy, M. V. R.; Brown, H. C. Tetrahedron Lett. 2004, 45, 1015. Ramachandran, P. V.; Prabhudas, B.; Chandra, J. S.; Reddy, M. V. R. J. Org. Chem. 2004, 69, 6294. Reddy, M. V. R.; Brown, H. C.; Ramachandran, P. V. J. Organomet. Chem. 2001, 624, 239. Bonini, C.; Chiummiento, L.; Pullez, M.; Solladie, G.; Colobert, F. J. Org. Chem. 2004, 69, 5015. Paterson, I.; Coster, M. J.; Chen, D. Y. M.; Gibson, K. R.; Wallace, D. J. Org. Biomol. Chem. 2005, 3, 2410. Ramachandran, P. V.; Chen, G. M.; Brown, H. C. Tetrahedron Lett. 1997, 38, 2417. Chen, G. M.; Ramachandran, P. V. Tetrahedron: Asymmetry 1997, 8, 3935. Bubnov, Y. N.; Lavrinovich, L. I.; Zykov, A. Y.; Ignatenko, A. V. Mendeleev Commun. 1992, 86. Ramachandran, P. V.; Krzeminski, M. P.; Reddy, M. V. R.; Brown, H. C. Tetrahedron: Asymmetry 1999, 10, 11. Trost, B. M.; Frederiksen, M. U.; Papillon, J. P. N.; Harrington, P. E.; Shin, S.; Shireman, B. T. J. Am. Chem. Soc. 2005, 127, 3666. Smith, A. B., III; Ott, G. R. J. Am. Chem. Soc. 1996, 118, 13095. Roush, W. R.; Palkowitz, A. D. J. Org. Chem. 1989, 54, 3009. Reddy, Y. K.; Falck, J. R. Org. Lett. 2002, 4, 969. Mikhailov, B. M.; Bubnov, Y. N. Russ. Chem. Bull. 1964, 13, 1774. Zhou, W.; Liang, S.; Yu, S.; Luo, W. J. Organomet. Chem. 1993, 452, 13. Paterson, I.; Wallace, D. J.; Gibson, K. R. Tetrahedron Lett. 1997, 38, 8911. White, J. B.; Blakemore, P. R.; Browder, C. C.; Hong, J.; Lincoln, C. M.; Nagornyy, P. A.; Robarge, L. A.; Wardrop, D. J. J. Am. Chem. Soc. 2001, 123, 8593. Dineen, T. A.; Roush, W. R. Org. Lett. 2004, 6, 2043. Smith, A. B., III; Safonov, I. G.; Corbett, R. M. J. Am. Chem. Soc. 2002, 124, 11102. Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123, 10942. Diez-Martin, D.; Kotecha, N. R.; Ley, S. V.; Mantegani, S.; Menendez, J. C.; Organ, H. M.; White, A. D.; Bank, B. J. Tetrahedron 1992, 48, 7899. Nicolaou, K. C.; Ahn, K. H. Tetrahedron Lett. 1989, 30, 1217. Smith, A. B., III; Lin, Q. L.; Nakayama, K.; Boldi, A. M.; Brook, C. S.; McBriar, M. D.; Moser, W. H.; Sobukawa, M.; Zhuang, L. Tetrahedron Lett. 1997, 38, 8675. Crimmins, M. T.; Washburn, D. G. Tetrahedron Lett. 1998, 39, 7487. Wu, Y. S.; Esser, L.; De Brabander, J. K. Angew. Chem., Int. Ed. 2000, 39, 4308. Shi, Y.; Peng, L. F.; Kishi, Y. J. Org. Chem. 1997, 62, 5666. Hoffmann, R. W.; Metternich, R.; Lanz, J. W. Liebigs Ann. Chem. 1987, 881. Thadani, A. N.; Batey, R. A. Tetrahedron Lett. 2003, 44, 8051. Roush, W. R.; Hunt, J. A. J. Org. Chem. 1995, 60, 798. Yakelis, N. A.; Roush, W. R. J. Org. Chem. 2003, 68, 3838. Pattenden, G.; Plowright, A. T. Tetrahedron Lett. 2000, 41, 983. Pattenden, G.; Gonzalez, M. A.; Little, P. B.; Millan, D. S.; Plowright, A. T.; Tornos, J. A.; Ye, T. Org. Biomol. Chem. 2003, 1, 4173.

ALLYLBORATION OF CARBONYL COMPOUNDS 280a 281 282 283

284

285 286 287

288 289

290 291

292 293 294

295

296 297 298 299 300

301 302 303 304 305 306 307

308

309 310 311 312

313 314

315 316 317 318

319 320

561

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332 333 334 335 336 337

338 339

340 341 342 343 344

345 346 347 348

349 350 351 352 353 354

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360 361 362 363

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ALLYLBORATION OF CARBONYL COMPOUNDS 364

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366 367 368 369 370 371 372 373 374 375 376 377 378 379 380 381 382 383 384

385 386 387 388 389 390 391 392 393 394 395 396 397 398 399

400 401 402

403 404

405 406 407 408

409 410

563

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564 411 412 413 414 415

416 417

418 419

420 421 422 423

424 425 426 427 428 429 430 431 432 433 434 435 436

437 438 439 440 441 442 443 444 445

446 447 448 449

450 451 452

453

454

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ALLYLBORATION OF CARBONYL COMPOUNDS 455 456 457 458 459 460 461 462 463 464 465

466 467

468

469 470 471 472 473 474

475 476 477 478 479 480

481 482 483

484 485 486 487

488 489 490 491

492 493

494

495

496 497

565

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566 498 499

500

501 502 503

504 505

506 507 508 509 510

511

512

513

514 515

516 517 518 519

520 521 522

523 524 525

526 527

528 529 530

531 532 533

534 535

ORGANIC REACTIONS

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ALLYLBORATION OF CARBONYL COMPOUNDS 536

537 538 539 540 541 542

543 544 545 546 547 548 549 550 551 552 553 554 555 556 557 558 559

560 561

562 563 564 565 566 567

568

569 570 571 572

573

574

575

576

577 578

567

Zampella, A.; Bassarello, C.; Bifulco, G.; Gomez-Paloma, L.; D’Auria, M. V. Eur. J. Org. Chem. 2002, 785. Roush, W. R.; Adam, M. A.; Harris, D. J. J. Org. Chem. 1985, 50, 2000. Brown, H. C.; Bhat, K. S.; Randad, R. S. J. Org. Chem. 1987, 52, 3701. Hoffmann, R. W.; Brinkmann, H.; Frenking, G. Chem. Ber. 1990, 123, 2387. Hoffmann, R. W.; Zeiss, H. J. Angew. Chem., Int. Ed. Engl. 1980, 19, 218. Roux, F.; Maugras, I.; Poncet, J.; Niel, G.; Jouin, P. Tetrahedron 1994, 50, 5345. Terauchi, T.; Morita, M.; Kimijima, K.; Nakamura, Y.; Hayashi, G.; Tanaka, T.; Kanoh, N.; Nakata, M. Tetrahedron Lett. 2001, 42, 5505. Kobayashi, Y.; Lee, J.; Tezuka, K.; Kishi, Y. Org. Lett. 1999, 1, 2177. Monica, C. D.; Maulucci, N.; De Riccardis, F.; Izzo, I. Tetrahedron: Asymmetry 2003, 14, 3371. Wuts, P. G.; Bigelow, S. S. J. Org. Chem. 1988, 53, 5023. Moret, E.; Schlosser, M. Tetrahedron Lett. 1984, 25, 4491. Lipomi, D. J.; Langille, N. F.; Panek, J. S. Org. Lett. 2004, 6, 3533. Roush, W. R.; Brown, B. B.; Drozda, S. E. Tetrahedron Lett. 1988, 29, 3541. Roush, W. R.; Brown, B. B. J. Am. Chem. Soc. 1993, 115, 2268. Satoh, M.; Nomoto, Y.; Miyaura, N.; Suzuki, A. Tetrahedron Lett. 1989, 30, 3789. Wang, X.; Porco, J., J. A. Angew. Chem., Int. Ed. 2005, 44, 3067. Nakata, M.; Ishiyama, T.; Akamatsu, S.; Suzuki, R.; Tatsuta, K. Synlett 1994, 601. Chemler, S. R.; Roush, W. R. J. Org. Chem. 2003, 68, 1319. Turk, J. A.; Visbal, G. S.; Lipton, M. A. J. Org. Chem. 2003, 68, 7841. Burke, S. D.; Hong, J.; Lennox, J. R.; Mongin, A. P. J. Org. Chem. 1998, 63, 6952. Cundy, D. J.; Donohue, A. C.; McCarthy, T. D. J. Chem. Soc., Perkin Trans. 1 1999, 559. Bauer, S. M.; Armstrong, R. W. J. Am. Chem. Soc. 1999, 121, 6355. Cundy, D. J.; Donohue, A. C.; McCarthy, T. D. Tetrahedron Lett. 1998, 39, 5125. Zheng, W. J.; DeMattei, J. A.; Wu, J. P.; Duan, J. J. W.; Cook, L. R.; Oinuma, H.; Kishi, Y. J. Am. Chem. Soc. 1996, 118, 7946. Knapp, S.; Dong, Y. Tetrahedron Lett. 1997, 38, 3813. Ireland, R. E.; Armstrong, J. D.; Lebreton, J.; Meissner, R. S.; Rizzacasa, M. A. J. Am. Chem. Soc. 1993, 115, 7152. Andrus, M. B.; Schreiber, S. L. J. Am. Chem. Soc. 1993, 115, 10420. Ireland, R. E.; Gleason, J. L.; Gegnas, L. D.; Highsmith, T. K. J. Org. Chem. 1996, 61, 6856. White, J. D.; Toske, S. G.; Yakura, T. Synlett 1994, 591. Hermitage, S. A.; Roberts, S. M.; Watson, D. J. Tetrahedron Lett. 1998, 39, 3567. Inoue, M.; Yamashita, S.; Tatami, A.; Miyazaki, K.; Hirama, M. J. Org. Chem. 2004, 69, 2797. Uehara, H.; Oishi, T.; Inoue, M.; Shoji, M.; Nagumo, Y.; Kosaka, M.; Le Brazidec, J. Y.; Hirama, M. Tetrahedron 2002, 58, 6493. Oishi, T.; Nagumo, Y.; Shoji, M.; Le Brazidec, J. Y.; Uehara, H.; Hirama, M. Chem. Commun. 1999. Tatami, A.; Inoue, M.; Uehara, H.; Hirama, M. Tetrahedron Lett. 2003, 44, 5229. Inoue, M.; Hirama, M. Synlett 2004, 577. Jiang, X.; Garc´ıa-Fortanet, J. G.; De Brabander, J. K. J. Am. Chem. Soc. 2005, 127, 11254. Smith, A. B., III; Adams, C. M.; Kozmin, S. A.; Paone, D. V. J. Am. Chem. Soc. 2001, 123, 5925. Nicolaou, K. C.; Murphy, F.; Barluenga, S.; Ohshima, T.; Wei, H.; Xu, J.; Gray, D. L. F.; Baudoin, O. J. Am. Chem. Soc. 2000, 122, 3830. Nicolaou, K. C.; Xu, J. Y.; Murphy, F.; Barluenga, S.; Baudoin, O.; Wei, H. X.; Gray, D. L. F.; Ohshima, T. Angew. Chem., Int. Ed. 1999, 38, 2447. Paterson, I.; Cumming, J. G.; Smith, J. D.; Ward, R. A.; Yeung, K. S. Tetrahedron Lett. 1994, 35, 3405. Paterson, I.; Ward, R. A.; Smith, J. D.; Cumming, J. G.; Yeung, K. S. Tetrahedron 1995, 51, 9437. Yamamoto, Y.; Yatagai, H.; Maruyama, K. J. Am. Chem. Soc. 1981, 103, 1969. Oikawa, M.; Ueno, T.; Oikawa, H.; Ichihara, A. J. Org. Chem. 1995, 60, 5048.

568 579 580 581 582

583 584 585 586

587 588

589 590 591 592 593

594

595

596 597 598 599 600 601 602 603 604

605 606 607 608

609 610 611 612 613 614

615

616 617

618 619

ORGANIC REACTIONS

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ALLYLBORATION OF CARBONYL COMPOUNDS 620 621 622 623 624 625 626

627 628 629

630 631 632

633 634 635 636 637 638 639 640 641 642 643 644 645 646 647

648 649 650 651 652 653

654 655 656 657 658 659 660 661

662

663 664

569

Williams, D. R.; Rojas, C. M.; Bogen, S. L. J. Org. Chem. 1999, 64, 736. Smith, A. B., III; Zheng, J. Tetrahedron 2002, 58, 6455. Smith, A. B., III; Zheng, J. Synlett 2001, 1019. Ooi, H.; Ishibashi, N.; Iwabuchi, Y.; Ishihara, J.; Hatakeyama, S. J. Org. Chem. 2004, 69, 7765. Kang, S. H.; Kim, C. M. Synlett 1996, 515. Roush, W. R.; Bannister, T. D. Tetrahedron Lett. 1992, 33, 3587. Roush, W. R.; Bannister, T. D.; Wendt, M. D.; Jablonowski, J. A.; Scheidt, K. A. J. Org. Chem. 2002, 67, 4275. Kende, A. S.; Koch, K.; Dorey, G.; Kaldor, I.; Liu, K. J. Am. Chem. Soc. 1993, 115, 9842. Andersen, M. W.; Hildebrandt, B.; Hoffmann, R. W. Angew. Chem., Int. Ed. Engl. 1991, 30, 97. Oikawa, H.; Yoneta, Y.; Ueno, T.; Oikawa, M.; Wakayama, T.; Ichihara, A. Tetrahedron Lett. 1997, 38, 7897. Oikawa, H. Curr. Med. Chem. 2002, 9, 2033. Paterson, I.; Anderson, E. A.; Dalby, S. M.; Loiseleur, O. Org. Lett. 2005, 7, 4121. Fisher, M. J.; Myers, C. D.; Joglar, J.; Chen, S. H.; Danishefsky, S. J. J. Org. Chem. 1991, 56, 5826. Labrecque, D.; Charron, S.; Rej, R.; Blais, C.; Lamothe, S. Tetrahedron Lett. 2001, 42, 2645. Barrett, A. G. M.; Lebold, S. A. J. Org. Chem. 1991, 56, 4875. Barrett, A. G. M.; Lebold, S. A. J. Org. Chem. 1990, 55, 5818. Sebelius, S.; Wallner, O. A.; Szab´o, K. J. Org. Lett. 2003, 5, 3065. Dineen, T. A.; Roush, W. R. Org. Lett. 2003, 5, 4725. Maurer, K. W.; Armstrong, R. W. J. Org. Chem. 1996, 61, 3106. Lin, G. Q.; Xu, W. C. Tetrahedron 1996, 52, 5907. Kang, S. H.; Jun, H. S.; Youn, J. H. Synlett 1998, 1045. Zampella, A.; Sepe, V.; D’Orsi, R.; D’Auria, M. V. Lett. Org. Chem. 2004, 308. Hori, K.; Kazuno, H.; Nomura, K.; Yoshii, E. Tetrahedron Lett. 1993, 34, 2183. Harada, T.; Kagamihara, Y.; Tanaka, S.; Sakamoto, K.; Oku, A. J. Org. Chem. 1992, 57, 1637. White, J. D.; Johnston, A. T. J. Org. Chem. 1994, 59, 3347. White, J. D.; Johnston, A. T. J. Org. Chem. 1990, 55, 5938. Hoffmann, R. W.; G¨ottlich, R.; Schopfer, U. Eur. J. Org. Chem. 2001, 1865. Chen, S. H.; Horvath, R. F.; Joglar, J.; Fisher, M. J.; Danishefsky, S. J. J. Org. Chem. 1991, 56, 5834. May, S. A.; Grieco, P. A. Chem. Commun. 1998, 1597. Tatsuta, K.; Ishiyama, T.; Tajima, S.; Koguchi, Y.; Gunji, H. Tetrahedron Lett. 1990, 31, 709. Andrus, M. B.; Turner, T. M.; Sauna, Z. E.; Ambudkar, S. V. J. Org. Chem. 2000, 65, 4973. Hu, H. S.; Jayaraman, S.; Oehlschage, A. C. J. Org. Chem. 1998, 63, 8843. Roush, W. R.; Lane, G. C. Org. Lett. 1999, 1, 95. Smith, A. B., III; Adams, C. M.; Barbosa, S. A. L.; Degnan, A. P. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 12042. Roush, W. R.; Coffey, D. S.; Madar, D.; Palkowitz, A. D. J. Braz. Chem. Soc. 1996, 7, 327. Sengoku, T.; Arimoto, H.; Uemura, D. Chem. Commun. 2004, 1220. Andrus, M. B.; Lepore, S. D.; Turner, T. M. J. Am. Chem. Soc. 1997, 119, 12159. Akita, H.; Yamada, H.; Matsukura, H.; Nakata, T.; Oishi, T. Tetrahedron Lett. 1990, 31, 1735. Oishi, T.; Akita, H. J. Synth. Org. Chem. Jpn. 1991, 49, 657. Zeng, X.; Zeng, F.; Negishi, E. Org. Lett. 2004, 6, 3245. Andrus, M. B.; Lepore, S. D. J. Am. Chem. Soc. 1997, 119, 2327. Nagamitsu, T.; Sunazuka, T.; Tanaka, H.; Omura, S.; Sprengeler, P. A.; Smith, A. B., III J. Am. Chem. Soc. 1996, 118, 3584. Sunazuka, T.; Nagamitsu, T.; Matsuzaki, K.; Tanaka, H.; Omura, S.; Smith, A. B., III J. Am. Chem. Soc. 1993, 115, 5302. Kohyama, N.; Yamamoto, Y. Synlett 2001, 694. Danishefsky, S. J.; Armistead, D. M.; Wincott, F. E.; Selnick, H. G.; Hungate, R. J. Am. Chem. Soc. 1989, 111, 2967.

570 665

666 667 668 669 670 671

672 673 674 675 676 677 678 679 680 681 682 683 684 685 686

687 688 689 690 691 692 693 694 695 696 697 698 699 700 701 702

703 704

705 706 707 708 709 710 711 712 713

ORGANIC REACTIONS

Danishefsky, S. J.; Armistead, D. M.; Wincott, F. E.; Selnick, H. G.; Hungate, R. J. Am. Chem. Soc. 1987, 109, 8117. Liu, B.; Zhou, W. S. Tetrahedron 2003, 59, 3379. Liu, B.; Zhou, W. Tetrahedron Lett. 2002, 43, 4187. Hoffmann, R. W.; Landmann, B. Tetrahedron Lett. 1983, 24, 3209. Hoffmann, R. W.; Landmann, B. Angew. Chem., Int. Ed. Engl. 1984, 23, 437. Mandal, A. K.; Schneekloth, J., J. S.; Crews, C. M. Org. Lett. 2005, 7, 3645. Yang, Z.; He, Y.; Vourloumis, D.; Vallberg, H.; Nicolaou, K. C. Angew. Chem., Int. Ed. Engl. 1997, 36, 166. Schlapbach, A.; Hoffmann, R. W. Eur. J. Org. Chem. 2001, 323. Hoffmann, R. W.; Schlapbach, A. Liebigs Ann. Chem. 1991, 1203. Midland, M. M.; Preston, S. B. J. Am. Chem. Soc. 1982, 104, 2330. Shimizu, M.; Kitagawa, H.; Kurahashi, T.; Hiyama, T. Angew. Chem., Int. Ed. 2001, 40, 4283. Andersen, M. W.; Hildebrandt, B.; Koster, G.; Hoffmann, R. W. Chem. Ber. 1989, 122, 1777. Zheng, B.; Srebnik, M. J. Org. Chem. 1995, 60, 486. Hoffmann, R. W.; Dahmann, G.; Andersen, M. W. Synthesis 1994, 629. Hoffmann, R. W.; Dahmann, G. Tetrahedron Lett. 1993, 34, 1115. Lombardo, M.; Morganti, S.; Trombini, C. J. Org. Chem. 2000, 65, 8767. Hoffmann, R. W.; St¨urmer, R. Chem. Ber. 1994, 127, 2511. Yamamoto, Y.; Yatagai, H.; Maruyama, K. J. Am. Chem. Soc. 1981, 103, 3229. Andemichael, Y. W.; Wang, K. K. J. Org. Chem. 1992, 57, 796. Wang, K. K.; Gu, G.; Liu, C. J. Am. Chem. Soc. 1990, 112, 4424. Yamaguchi, M.; Mukaiyama, T. Chem. Lett. 1980, 993. Patron, A. P.; Richter, P. K.; Tomaszewski, M. J.; Miller, R. A.; Nicolaou, K. C. J. Chem. Soc., Chem. Commun. 1994, 1147. Hoffmann, R. W.; Rolle, U.; G¨ottlich, R. Liebigs Ann. Chem. 1996, 1717. St¨urmer, R.; Ritter, K.; Hoffmann, R. W. Angew. Chem., Int. Ed. Engl. 1993, 32, 101. Tsai, D. J. S.; Matteson, D. S. Organometallics 1983, 2, 236. Carosi, L.; Lachance, H.; Hall, D. G. Tetrahedron Lett. 2005, 46, 8981. Beckmann, E.; Desai, V.; Hoppe, D. Synlett 2004, 2275. Yamamoto, Y.; Saito, Y.; Maruyama, K. J. Org. Chem. 1983, 48, 5408. Hoffmann, R. W.; Ladner, W.; Ditrich, K. Liebigs Ann. Chem. 1989, 883. Hoffmann, R. W.; Rolle, U. Tetrahedron Lett. 1994, 35, 4751. Hoffmann, R. W.; Haeberlin, E.; Rohde, T. Synthesis 2002, 207. St¨urmer, R.; Hoffmann, R. W. Chem. Ber. 1994, 127, 2519. Brown, H. C.; Jadhav, P. K.; Perumal, P. T. Tetrahedron Lett. 1984, 25, 5111. Bubnov, Y. N.; Etinger, M. Y. Tetrahedron Lett. 1985, 26, 2797. Brown, H. C.; Randad, R. S. Tetrahedron 1990, 46, 4463. Brown, H. C.; Randad, R. S. Tetrahedron Lett. 1990, 31, 455. Salunkhe, A. M.; Ramachandran, P. V.; Brown, H. C. Tetrahedron Lett. 1999, 40, 1433. Gurskii, M. E.; Golovin, S. B.; Ignatenko, A. V.; Bubnov, Y. N. Russ. Chem. Bull. 1993, 42, 139. Chataigner, I.; Lebreton, J.; Zammattio, F.; Villieras, J. Tetrahedron Lett. 1997, 38, 3719. van der Heide, T. A. J.; van der Baan, J. L.; Bijpost, E. A.; de Kanter, F. J. J.; Bickelhaupt, F.; Klumpp, G. W. Tetrahedron Lett. 1993, 34, 4655. Barrett, A. G. M.; Braddock, D. C.; de Koning, P. D. Chem. Commun. 1999, 459. Gurskii, M. E.; Golovin, S. B.; Bubnov, Y. N. Russ. Chem. Bull. 1990, 39, 433. Barrett, A. G. M.; Wan, P. W. H. J. Org. Chem. 1996, 61, 8667. Williams, D. R.; Meyer, K. G.; Shamim, K.; Patnaik, S. Can. J. Chem. 2004, 82, 120. Hara, S.; Suzuki, A. Tetrahedron Lett. 1991, 32, 6749. Williams, D. R.; Brooks, D. A.; Meyer, K. G.; Clark, M. P. Tetrahedron Lett. 1998, 39, 7251. Yamamoto, Y.; Hara, S.; Suzuki, A. Synth. Commun. 1997, 27, 1029. Hara, S.; Yamamoto, Y.; Fujita, A.; Suzuki, A. Synlett 1994, 639. Draillard, K.; Lebreton, J.; Villieras, J. Tetrahedron: Asymmetry 1999, 10, 4281.

ALLYLBORATION OF CARBONYL COMPOUNDS 714 715 716

717

718 719 720 721 722 723 724 725 726 727 728

729 730 731 732

733 734 735 736 737 738 739 740 741 742

743 744 745 746 747 748 749 750 751 752 753 754 755 756 757 758

759 760

571

Brzezinski, L. J.; Leahy, J. W. Tetrahedron Lett. 1998, 39, 2039. Williams, D. R.; Clark, M. P.; Berliner, M. A. Tetrahedron Lett. 1999, 40, 2287. Williams, D. R.; Kiryanov, A. A.; Emde, U.; Clark, M. P.; Berliner, M. A.; Reeves, J. T. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 12058. Williams, D. R.; Kiryanov, A. A.; Emde, U.; Clark, M. P.; Berliner, M. A.; Reeves, J. T. Angew. Chem., Int. Ed. 2003, 42, 1258. Ishiyama, T.; Kitano, T.; Miyaura, N. Tetrahedron Lett. 1998, 39, 2357. Goujon, J. Y.; Zammattio, F.; Chretien, J. M.; Beaudet, I. Tetrahedron 2004, 60, 4037. Williams, D. R.; Clark, M. P.; Emde, U.; Berliner, M. A. Org. Lett. 2000, 2, 3023. Williams, D. R.; Meyer, K. G. J. Am. Chem. Soc. 2001, 123, 765. Zhai, H. B.; Luo, S. J.; Ye, C. F.; Ma, Y. X. J. Org. Chem. 2003, 68, 8268. Williams, D. R.; Patnaik, S.; Plummer, S. V. Org. Lett. 2003, 5, 5035. Williams, D. R.; Brooks, D. A.; Berliner, M. A. J. Am. Chem. Soc. 1999, 121, 4924. Corey, E. J.; Huang, H. C. Tetrahedron Lett. 1989, 30, 5235. Kim, S.; Sutton, S. C.; Guo, C.; LaCour, T. G.; Fuchs, P. L. J. Am. Chem. Soc. 1999, 121, 2056. Kim, S. K.; Sutton, S. C.; Fuchs, P. L. Tetrahedron Lett. 1995, 36, 2427. Thaper, R. K.; Zykov, A. Y.; Bubnov, Y. N.; Reshetova, I. G.; Kamernitsky, A. V. Synth. Commun. 1993, 23, 939. Jernelius, J. A.; Schrock, R. R.; Hoveyda, A. H. Tetrahedron 2004, 60, 7345. Barrett, A. G. M.; Seefeld, M. A. Tetrahedron 1993, 49, 7857. Barrett, A. G. M.; Seefeld, M. A. J. Chem. Soc., Chem. Commun. 1993, 339. Gurskii, M. E.; Geiderickh, A. V.; Ignatenko, A. V.; Bubnov, Y. N. Russ. Chem. Bull. 1993, 42, 144. Narla, G.; Brown, H. C. Tetrahedron Lett. 1997, 38, 219. Roush, W. R.; Pinchuk, A. N.; Micalizio, G. C. Tetrahedron Lett. 2000, 41, 9413. Wang, K. K.; Liu, C. J. Org. Chem. 1986, 51, 4733. Wang, K. K.; Liu, C.; Gu, Y. G.; Burnett, F. N.; Sattsangi, P. D. J. Org. Chem. 1991, 56, 1914. Hoffmann, R. W.; Kemper, B. Tetrahedron Lett. 1980, 21, 4883. Brown, H. C.; Phadke, A. S. Synlett 1993, 927. Hoffmann, R. W.; Metternich, R. Liebigs Ann. Chem. 1985, 2390. Yamamoto, Y.; Hara, S.; Suzuki, A. Synlett 1996, 883. Soundararajan, R.; Li, G. S.; Brown, H. C. J. Org. Chem. 1996, 61, 100. Barrett, A. G. M.; Beall, J. C.; Braddock, D. C.; Flack, K.; Gibson, V. C.; Salter, M. M. J. Org. Chem. 2000, 65, 6508. Micalizio, G. C.; Roush, W. R. Org. Lett. 2000, 2, 461. Soundararajan, R.; Li, G.; Brown, H. C. Tetrahedron Lett. 1995, 36, 2441. Coleman, R. S. Synlett 1998, 1031. Barrett, A. G. M.; Seefeld, M. A.; White, A. J. P.; Williams, D. J. J. Org. Chem. 1996, 61, 2677. Ganesh, P.; Nicholas, K. M. J. Org. Chem. 1997, 62, 1737. Wang, X.; Porco, J. A. J. Am. Chem. Soc. 2003, 125, 6040. Schinzer, D.; Limberg, A.; Bohm, O. M. Chem. Eur. J. 1996, 2, 1477. Wuts, P. G. M.; Bigelow, S. S. J. Org. Chem. 1983, 48, 3489. Gaddoni, L.; Lombardo, M.; Trombini, C. Tetrahedron Lett. 1998, 39, 7571. Barrett, A. G. M.; Malecha, J. W. J. Chem. Soc., Perkin Trans. 1 1994, 1901. Hertweck, C.; Boland, W. J. Org. Chem. 1999, 64, 4426. Hertweck, C.; Goerls, H.; Boland, W. Chem. Commun. 1998, 1955. Roush, W. R.; Michaelides, M. R. Tetrahedron Lett. 1986, 27, 3353. Hu, S. J.; Jayaraman, S.; Oehlschlager, A. C. J. Org. Chem. 1998, 63, 8843. Hunt, J. A.; Roush, W. R. Tetrahedron Lett. 1995, 36, 501. Roush, W. R.; Grover, P. T.; Marron, T. G. In Current Topics in the Chemistry of Boron, Proceedings of the Eighth International Meeting, Knoxville, Tennessee, 1993; Kabalka, G. W., Ed.; Royal Society of Chemistry: Cambridge, U.K., 1994. Roush, W. R.; Follows, B. C. Tetrahedron Lett. 1994, 35, 4935. Heo, J. N.; Micalizio, G. C.; Roush, W. R. Org. Lett. 2003, 5, 1693.

572 761 762 763 764

765 766

767

768 769

770

771 772 773 774 775

776 777 778 779 780 781 782

783 784 785 786 787 788 789 790 791 792 793 794

795

796 797 798 799 800 801 802 803 804 805

ORGANIC REACTIONS

Chang, K. J.; Rayabarapu, D. K.; Yang, F. Y.; Cheng, C. H. J. Am. Chem. Soc. 2005, 127, 126. Jayaraman, S.; Hu, S.; Oehlschlager, A. C. Tetrahedron Lett. 1995, 36, 4765. Micalizio, G. C.; Pinchuk, A. N.; Roush, W. R. J. Org. Chem. 2000, 65, 8730. Barrett, A. G. M.; Bennett, A. J.; Menzer, S.; Smith, M. L.; White, A. J. P.; Williams, D. J. J. Org. Chem. 1999, 64, 162. Barluenga, S.; Lopez, P.; Moulin, E.; Winssinger, N. Angew. Chem., Int. Ed. 2004, 43, 3467. Roush, W. R.; Michaelides, M. R.; Tai, D. F.; Chong, W. K. M. J. Am. Chem. Soc. 1987, 109, 7575. Roush, W. R.; Michaelides, M. R.; Tai, D. F.; Lesur, B. M.; Chong, W. K. M.; Harris, D. J. J. Am. Chem. Soc. 1989, 111, 2984. Roush, W. R.; Harris, D. J.; Lesur, B. M. Tetrahedron Lett. 1983, 24, 2227. Smith, A. L.; Pitsinos, E. N.; Hwang, C. K.; Mizuno, Y.; Saimoto, H.; Scarlato, G. R.; Suzuki, T.; Nicolaou, K. C. J. Am. Chem. Soc. 1993, 115, 7612. Smith, A. L.; Hwang, C. K.; Pitsinos, E.; Scarlato, G. R.; Nicolaou, K. C. J. Am. Chem. Soc. 1992, 114, 3134. Burgess, K.; Henderson, I. Tetrahedron Lett. 1990, 31, 6949. Sato, M.; Yamamoto, Y.; Hara, S.; Suzuki, A. Tetrahedron Lett. 1993, 34, 7071. Duan, J. J. W.; Smith, A. B., III J. Org. Chem. 1993, 58, 3703. Heo, J. N.; Holson, E. B.; Roush, W. R. Org. Lett. 2003, 5, 1697. Burgess, K.; Chaplin, D. A.; Henderson, I.; Pan, Y. T.; Elbein, A. D. J. Org. Chem. 1992, 57, 1103. Jadhav, P. K.; Woemer, F. J. Tetrahedron Lett. 1994, 35, 8973. Gu, Y. G.; Wang, K. K. Tetrahedron Lett. 1991, 32, 3029. Sutherlin, D. P.; Armstrong, R. W. Tetrahedron Lett. 1993, 34, 4897. Kim, J. D.; Kim, I. S.; Hua, J. C.; Zee, O. P.; Jung, Y. H. Tetrahedron Lett. 2005, 46, 1079. Moriya, T.; Suzuki, A.; Miyaura, N. Tetrahedron Lett. 1995, 36, 1887. Suginome, M.; Nakamura, H.; Matsuda, T.; Ito, Y. J. Am. Chem. Soc. 1998, 120, 4248. Ramachandran, P. V.; Pratihar, D.; Biswas, D.; Srivastava, A.; Reddy, M. V. R. Org. Lett. 2004, 6, 481. Yamamoto, Y.; Yatagai, H.; Maruyama, K. J. Chem. Soc., Chem. Commun. 1980, 1072. Kabalka, G. W.; Venkataiah, B.; Dong, G. J. Org. Chem. 2004, 69, 5807. Kabalka, G. W.; Venkataiah, B.; Dong, G. Tetrahedron Lett. 2005, 46, 4209. Coleman, R. S.; Gurrala, S. R.; Mitra, S.; Raao, A. J. Org. Chem. 2005, 70, 8932. Coleman, R. S.; Gurrala, S. R. Org. Lett. 2005, 7, 1849. Micalizio, G. C.; Roush, W. R. Org. Lett. 2001, 3, 1949. Hertweck, C.; Boland, W. Tetrahedron 1997, 53, 14651. Hertweck, C.; Boland, W. J. Org. Chem. 2000, 65, 2458. Suginome, M.; Yamamoto, Y.; Fujii, K.; Ito, Y. J. Am. Chem. Soc. 1995, 117, 9608. Jadhav, P. K.; Man, H. W. Tetrahedron Lett. 1996, 37, 1153. Taylor, R. E.; Hearn, B. R.; Ciavarri, J. P. Org. Lett. 2002, 4, 2953. Nakata, M.; Osumi, T.; Ueno, A.; Kimura, T.; Tamai, T.; Tatsuta, K. Tetrahedron Lett. 1991, 32, 6015. Nakata, M.; Osumi, T.; Ueno, A.; Kimura, T.; Tamai, T.; Tatsuta, K. Bull. Chem. Soc. Jpn. 1992, 65, 2974. Zhang, Q.; Lu, H.; Richard, C.; Curran, D. P. J. Am. Chem. Soc. 2004, 126, 36. Kabalka, G. W.; Venkataiah, B. Tetrahedron Lett. 2005, 46, 7325. Carter, K. D.; Panek, J. S. Org. Lett. 2004, 6, 55. Harried, S. S.; Lee, C. P.; Yang, G.; Lee, T. I. H.; Myles, D. C. J. Org. Chem. 2003, 68, 6646. Harried, S. S.; Yang, G.; Strawn, M. A.; Myles, D. C. J. Org. Chem. 1997, 62, 6098. Zakarian, A.; Batch, A.; Holton, R. A. J. Am. Chem. Soc. 2003, 125, 7822. Carri´e, D.; Carboni, B.; Vaultier, M. Tetrahedron Lett. 1995, 36, 8209. Favre, E.; Gaudemar, M. J. Organomet. Chem. 1975, 92, 17. Kulkarni, S. V.; Brown, H. C. Tetrahedron Lett. 1996, 37, 4125. Brown, H. C.; Khire, U. R.; Narla, G. J. Org. Chem. 1995, 60, 8130.

ALLYLBORATION OF CARBONYL COMPOUNDS 806 807 808 809 810 811 812 813 814 815 816 817 818 819 820 821 822 823 824 825 826 827 828 829 830 831 832 833 834

573

Hernandez, E.; Soderquist, J. A. Org. Lett. 2005, 7, 5397. Zweifel, G.; Backlund, S. J.; Leung, T. J. Am. Chem. Soc. 1978, 100, 5561. Brown, H. C.; Khire, U. R.; Racherla, U. S. Tetrahedron Lett. 1993, 34, 15. Brown, H. C.; Khire, U. R.; Narla, G.; Racherla, U. S. J. Org. Chem. 1995, 60, 544. Favre, E.; Gaudemar, M. J. Organomet. Chem. 1974, 76, 297. Wang, K. K.; Nikam, S. S.; Ho, C. D. J. Org. Chem. 1983, 48, 5376. Maddess, M. L.; Lautens, M. Org. Lett. 2005, 7, 3557. Ikeda, N.; Arai, I.; Yamamoto, H. J. Am. Chem. Soc. 1986, 108, 483. Favre, E.; Gaudemar, M. J. Organomet. Chem. 1974, 76, 305. Wang, K. K.; Liu, C. J. Org. Chem. 1985, 50, 2578. Corey, E. J.; Jones, G. B. Tetrahedron Lett. 1991, 32, 5713. Matsumoto, Y.; Naito, M.; Uozumi, Y.; Hayashi, T. J. Chem. Soc., Chem. Commun. 1993, 1468. Hilt, G.; Luers, S.; Smolko, K. I. Org. Lett. 2005, 7, 251. Herberich, G. E.; Englert, U.; Wang, S. Chem. Ber. 1993, 126, 297. Brown, H. C.; Bhat, K. S.; Jadhav, P. K. J. Chem. Soc., Perkin Trans. 1 1991, 2633. Lallemand, J. Y.; Six, Y.; Ricard, L. Eur. J. Org. Chem. 2002, 503. Renard, J. Y.; Lallemand, J. Y. Bull. Soc. Chim. Fr. 1996, 133, 143. Renard, P. Y.; Lallemand, J. Y. Tetrahedron: Asymmetry 1996, 7, 2523. Ohanessian, G.; Six, Y.; Lallemand, J. Y. Bull. Soc. Chim. Fr. 1996, 133, 1143. Gao, X.; Hall, D. G. Tetrahedron Lett. 2003, 44, 2231. Schleth, F.; Vogler, T.; Harms, K.; Studer, A. Chem. Eur. J. 2004, 10, 4171. Brown, H. C.; Jayaraman, S. Tetrahedron Lett. 1993, 34, 3997. Deligny, M.; Carreaux, F.; Carboni, B.; Toupet, L.; Dujardin, G. Chem. Commun. 2003, 276. Deligny, M.; Carreaux, F.; Carboni, B. Synlett 2005, 1462. Grieco, P. A.; Dai, Y. J. J. Am. Chem. Soc. 1998, 120, 5128. Hoffmann, R. W.; Munster, I. Tetrahedron Lett. 1995, 36, 1431. Hoffmann, R. W.; Munster, I. Liebigs Ann. Rec. 1997, 1143. Hoffmann, R. W.; Sander, T. Liebigs Ann. Chem. 1993, 1185. Kruger, J.; Hoffmann, R. W. J. Am. Chem. Soc. 1997, 119, 7499.

AUTHOR INDEX, VOLUMES 1-73

Volume number only is designated in this index

Adam, Waldemar, 61, 69 Adams, Joe T., 8 Adkins, Homer, 8 Agenet, Nicolas, 68 Ager, David J., 38 Albertson, Noel F., 12 Allen, George R., Jr., 20 Angyal, S. J., 8 Antoulinkis, Evan G., 57 Alonso, Diego A., 72 Apparu, Marcel, 29 Archer, S., 14 Arseniyadis, Simeon, 31 Aubert, Corinne, 68

Boswell, G. A., Jr., 21 Brand, William W., 18 Brewster, James H., 7 Brown, Herbert C , 13 Brown, Weldon G., 6 Bruson, Herman Alexander, 5 Bublitz, Donald E., 17 Buck, Johannes S., 4 Bufali, Simone, 68 Buisine, Olivier, 68 Burke, Steven D., 26 Butz, Lewis W., 5 Cahard, Dominique, 69 Caine, Drury, 23 Cairns, Theodore L., 20 Carmack, Marvin, 3 Carpenter, Nancy E., 66 Carreira, Eric M., 67 Carter, H. E., 3 Cason, James, 4 Castro, Bertrand R., 29 Casy, Guy, 62 Chamberlin, A. Richard, 39 Chapdelaine, Marc J., 38 Charette, Andrd B., 58 Chen, Bang-Chi, 62 Cheng, Chia-Chung, 28 Ciganek, Engelbert, 32, 51, 62, 72 Clark, Robin D., 47 Confalone, Pat N., 36 Cope, Arthur C , 9, 11 Corey, Elias J., 9 Cota, Donald J., 17

Bachmann, W. E., 1,2 Baer, Donald R., 11 Banfi, Luca, 65 Baudoux, J6r6me, 69 Baxter, Ellen W., 59 Beauchemin, Andre\ 58 Behr, Lyell C , 6 Behrman, E. J., 35 Bergmann, Ernst D., 10 Berliner, Ernst, 5 Biellmann, Jean-Francois, 27 Birch, Arthur J., 24 Blatchly, J. M., 19 Blatt, A. R , 1 Blicke, F. F., 1 Block, Eric, 30 Bloom, Steven H., 39 Bloomfield, Jordan J., 15, 23 Bonafoux, Dominique, 56

Organic Reactions, Vol. 73, Edited by Scott E. Denmark et al. © 2008 Organic Reactions, Inc. Published by John Wiley & Sons, Inc. 589

AUTHOR INDEX. VOLUMES 1-73

Cowden, Cameron J., 51 Crandall, Jack K., 29 Crich, David, 64 Crimmins, Michael T., 44 Crouch, R. David, 63 Crounse, Nathan N., 5

Govindachari, Tulicorin R., 6 Grieco, Paul A., 26 Grierson, David, 39 Gschwend, Heinz W., 26 Gung, Benjamin W., 64 Gutschc, C. David, 8

Daub, Guido H., 6 Dave, Vinod, 18 Davies, Huw M. L., 57 Davis, Franklin A., 62 Denmark, Scott E., 45 Denny, R. W., 20 DeLucchi, Ottorino, 40 DeTar, DeLos F., 9 Dickhaut, J., 48 Djerassi, Carl, 6 Donaruma, L. Guy, 11 Drake, Nathan L., 1 DuBois, Adrien S., 5 Ducep, Jean-Bernard, 27 Dunogues, Jacques, 37

Habermas, Karl L., 45 Hageman, Howard A.. 7 Hall, Dennis G., 73 Hamilton, Cliff S., 2 Hamlin, K. E., 9 Hanford, W. E., 3 Hanson, Robert M., 60 Harris, Constance M., 17 Harris, J. F., Jr., 13 Harris, Thomas M., 17 Hartung, Walter H., 7 Hassall, C. H., 9 Hauser, Charles R., 1,8 Hayakawa, Yoshihiro, 29 Heck, Richard F., 27 Hcldt, Walter Z., 11 Heintzelman, Geoffrey R., 65 Henne, Albert L., 2 Hofferberth, John E., 62 Hoffman, Roger A., 2 Hoiness, Connie M., 20 Holmes, H. L., 4, 9 Houlihan, William J., 16 House, Herbert O., 9 Hudlicky\ MiloS, 35 Hudlicky, TomaS, 33, 41 Hudson, Boyd E., Jr., 1 Hughes, David L., 42 Huie. E. M., 36 Hulce, Martin, 38 Huyscr, Earl S., 13 Hyatt, John A., 45

Eliel, Ernest L., 7 Emerson, William S., 4 Engel, Robert, 36 England, D. C. 6 Fan, Rulin, 41 Farina, Vitlorio, 50 Ferrier. Robert J., 62 Fettes, Alec, 67 Fieser. Louis F., 1 Fleming, Ian, 37 Folkcrs, Karl, 6 Fry, James L., 71 Fuson, Reynold C , 1 Gadamasetti, Kumar G., 41 Gandon, Vincent, 68 Gawley, Robert E., 35 Geissman, T. A., 2 Gcnslcr, Walter J., 6 Giese, B., 48 Gilman, Henry, 6, 8 Ginsburg, David, 10 Gobel, T., 48

Idacavage, Michael J.. 33 Idc, Walter S„ 4 Ingcrsoll, A. W.. 2 Itsuno, Shinichi, 52 Jackson, Ernest L., 2 Jacobs, Thomas L., 5 Jahangir, Alam, 47

AUTHOR INDEX. VOLUMES 1-73

Jakka. Kavitha. 69 Johnson, John R., I Johnson, Roy A., 63 Johnson, William S., 2. 6 Jones, Gurnos, 15, 49, 56 Jones, Reuben G., 6 Jones, Todd K., 45 Jorgenson, Margaret J., 18 Kanai, Motomu, 70 Kappe. C. Oliver, 63 Katsuki, Tsutomu, 48 Kende, Andrew S., 11 Kloctzcl, Milton C , 4 Knochel, Paul, 58 Kobayashi, Shu, 46 Kochi, Jay K., 19 Kopping, B., 48 Kornblum, Nathan, 2, 12 Kosolapoff, Gennady M., 6 Krcider, Eunice M., 18 Krimcn, L. L, 17 Krishnamurthy, Vcnkat, 50 Krow, Grant R., 43 Kuhlmann, Heinrich, 40 Kulickc, K. J.. 48 Kulka, Marshall, 7 Kutchan, Toni M., 33 Kyler, Keith S., 31 Lachance, Hugo, 73 Lane, John F., 3 Larson. Gerald L., 71 Leffler, Marl in T.. 1 Letavic. Michael A., 66 Lim, Linda B. L., 64 Link, J. T., 60 Little, R. Daniel, 47 Lipshutz. Bruce H., 41 Luzzio, Frederick A., 53 Malacria, Max, 68 McCombic, Stuart W., 66 McElvain. S. M., 4 McKeever, C. H., 1 McLoughlin, J. I., 47 McMurry, John E., 24 McOmie, J. F. W., 19

Maercker, Adalbert, 14 Magerlein, Barney J., 5 Mahajan. Yogesh R., 65 Malek, Jaroslav, 34, 36 Mallory, Clelia W., 30 Mallory, Frank B., 30 Manskc. Richard H. F., 7 Marcinow, Zbigniew, 42 Marti, Christiane, 67 Martin, Elmore L.. 1 Martin. Victor S., 48 Martin, William B., 14 Masjedizadeh, Mohammad R., Mcigh, Ivona R., 65 Meijcr, Egbert W., 28 Melikyan, G. G., 49 Mikami, Koichi, 46 Miller. Joseph A., 32 Millot, Nicolas, 58 Miotti. Umberto, 40 Mita, Tsuyoshi, 70 Modena, Giorgio, 40 Molander, Gary, 46 Moore, Maurice L., 5 Morgan, Jack F., 2 Moriarty, Robert M., 54, 57 Morton, John W., Jr., 8 Moscttig, Erich, 4, 8 Mozingo. Ralph, 4 Mukaiyama, Tcruaki, 28. 46

Nace, Harold R., 12 Nagata, Wataru, 25 Najera, Carmen, 72 Nakai, Takeshi, 46 Nakamura, Eiichi. 61 Naqvi. Saiyid M., 33 Negishi, Ei-Ichi, 33 Nelke, Janice M., 23 Nelson, Todd D., 63 Newman, Mclvin S., 5 Nickon, A., 20 Nielsen, Arnold T., 16 Noe, Mark C , 66 Noyori, Ryoji, 29

Ohno, Masaji, 37 Ojima. Iwao, 56

592

AUTHOR INDEX. VOLUMES 1-73

Otsuka, Masami. 37 Oveman, Larry E., 66 Owsley, Dennis C , 23 Pappo, Raphael, 10 Paquette, Leo A., 25, 62 Parham, William E., 13 Parmerter, Stanley M., 10 Pasto, Daniel J., 40 Patcrson, Ian, 51 Pettit, George R., 12 Phadke, Ragini, 7 Phillips, Robert R., 10 Picrini, Adriana B., 54 Pigge, F. Christopher, 51 Pine, Stanley H., 18,43 Pinnick, Harold W., 38 Porter, H. K., 20 Posner, Gary H., 19, 22 Prakash, Om, 54, 57 Price, Charles C . 3 Rabideau, Peter W., 42 Rabjohn, Norman, 5. 24 Rathke, Michael W., 22 Raulins, N. Rebecca, 22 Raynolds, Peter W., 45 Reed, Josephine W., 41 Reich, Hans J., 44 Rcinhold, Tracy L., 44 Reitz, Allen B., 59 Rhoads, Sara Jane, 22 Rickborn, Bruce. 52. 53 Rigby, James H., 49, 51 Rinehart, Kenneth L., Jr., 17 Ripka, W. C , 21 Riva, Renata. 65 Roberts, John D., 12 Rodriguez, Alain L., 58 Rodriguez, Herman R., 26 Roe, Arthur. 5 Rondcstvcdt, Christian S., Jr., 11, 24 Rossi, Roberto, 54 Ruh-Polenz, Carmen, 55 Rytina, Anton W., 5 Saha-Moller, Chantu R., 61 Santiago, Ana N., 54

Sauer, John C , 3 Schaefer, John P., 15 Schore, Neil E., 40 Schulenberg, J. W., 14 Schwcizcr, Edward E., 13 Scott, William J., 50 Scribner, R. M., 21 Seeberger. Peter H., 68 Scmmelhack, Martin F., 19 Sengupta, Saumitra, 41 Sethna, Suresh, 7 Shapiro, Robert H., 23 Sharts, Clay M., 12, 21 Sheehan, John C , 9 Sheldon, Roger A., 19 Sheppard. W. A., 21 Shibasaki, Masakatsu, 70 Shirley, David A., 8 Shriner, Ralph L„ 1 Simmons, Howard E., 20 Simonoff, Robert, 7 Slowinski, Franck, 68 Smith, Lee Irvin, 1 Smith, Peter A. S., 3, 11 Smithers, Roger, 37 Snow, Sheri L., 66 Spielman. M. A., 3 Spoerri, Paul E., 5 Stacey, F. W., 13 Stadler. Alexander, 63 Stanforth, Stephen P., 49, 56 Stcttcr, Hermann, 40 Struve, W. S., 1 Suter, C. M., 3 Swamer, Frederic W., 8 Swern, Daniel, 7

Takai, Kazuhiko, 64 Tarbell, D. Stanley, 2 Taylor. Richard J.K.. 62 Taylor, Richard T., 40 Thoma. G., 48 Tidwell. Thomas T., 39 Todd, David, 4 Toustcr, Oscar, 7 Trach, F., 48 Truce, William E., 9, 18 Trumbull, Elmer R., 11 Tsai, Chung-Ying, 56

AUTHOR INDEX, VOLUMES 1-73

Tucker. Charles E.. 58 Tullock, C. W„ 21 Tzamarioudaki, Maria. 56 Ucmura. Motokazu. 67

van Leusen. Albert M., 57 van Leusen. Daan, 57 van Tamclen, Eugene E., 12 Vcdejs, E., 22 Vladuchick. Susan A., 20 Vorbruggcn. Helmut. 55 Wadsworth, William S.. Jr., 25 Walling. Cheves, 13 Wallis, Everett S.. 3 Wallquist, Olof, 47 Wang, Chia-Lin L.. 34 WarnhoiT. E. W., 18 Waters. Marccy L., 70 Watt, David S., 31 Weinreb, Steven M., 65

Weston. Arthur W., 3. 9 Whalcy, Wilson ML, 6 Wilds, A. L., 2 Wiley, Richard H., 6 Williamson. David H., 24 Wilson, C. V., 9 Wilson. Stephen R.. 43 Wolf. Donald E.. 6 Wolff, Hans, 3 Wollowitz, Susan, 44 Wood. John L.. 3 Wulff, William D., 70 Wynberg, Hans, 28 Yamago, Shigcru. 61 Yan, Shou-Jcn. 28 Yoshioka, Mitsuru, 25 Zaugg. Harold E.. 8, 14 Zhao, Cong-Gui, 61, 69 Zhou. Ping, 62 Zubkov, Oleg A., 62 Zweifcl. George. 13, 32

593

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Many chapters contain brief discussions of reactions and comparisons of alternative synthetic methods related to the reaction that is the subject of the chapter. These related reactions and alternative methods are not usually listed in this index. In this index, the volume number is in boldface, the chapter number is in ordinary type. Acetoacetic ester condensation, 1, 9 Acetylenes: cotrimerizations of, 68, 1 oxidation by dioxirane, 69, 1 reactions with Fischer carbene complexes, phenol and quinone formation, 70, 2 synthesis of, 5, 1; 23, 3; 32, 2 Acid halides: reactions with esters, 1, 9 reactions with organometallic compounds, 8, 2 α-Acylamino acid mixed anhydrides, 12, 4 α-Acylamino acids, azlactonization of, 3, 5 Acylation: of esters with acid chlorides, 1, 9 intramolecular, to form cyclic ketones, 2, 4; 23, 2 of ketones to form diketones, 8, 3 Acyl fluorides, synthesis of, 21, 1; 34, 2; 35, 3 Acyl hypohalites, reactions of, 9, 5 Acyloins, 4, 4; 15, 1; 23, 2 Alcohols: conversion to fluorides, 21, 1, 2; 34, 2; 35, 3 conversion to olefins, 12, 2 oxidation of, 6, 5; 39, 3; 53, 1

replacement of hydroxy group by nucleophiles, 29, 1; 42, 2 resolution of, 2, 9 Alcohols, synthesis: by allylstannane addition to aldehydes, 64, 1 by base-promoted isomerization of epoxides, 29, 3 by hydroboration, 13, 1 by hydroxylation of ethylenic compounds, 7, 7 by organochromium reagents to carbonyl compounds, 64, 3 by reduction, 6, 10; 8, 1; 71, 1 from organoboranes, 33, 1; 73, 1 Aldehydes, additions of allyl, allenyl, propargyl stannanes, 64, 1 addition of allylic boron compounds, 73, 1 Aldehydes, catalyzed addition to double bonds, 40, 4 Aldehydes, synthesis of, 4, 7; 5, 10; 8, 4, 5; 9, 2; 33, 1 Aldol condensation, 16;67, 1 catalytic, enantioselective, 67, 1 directed, 28, 3 with boron enolates, 51, 1 Aliphatic fluorides, 2, 2; 21, 1, 2; 34, 2; 35, 3

Organic Reactions, Vol. 73, Edited by Scott E. Denmark et al.  2008 Organic Reactions, Inc. Published by John Wiley & Sons, Inc. 595

596

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Alkanes: by reduction of alkyl halides with organochromium reagents, 64, 3 of carbonyl groups with organosilanes, 71, 1 oxidation of, 69, 1 Alkenes: arylation of, 11, 3; 24, 3; 27, 2 asymmetric dihydroxylation, 66, 2 cyclopropanes from, 20, 1 cyclization in intramolecular Heck reactions 60, 2 from carbonyl compounds with organochromium reagents, 64, 3 dioxirane epoxidation of, 61, 2 epoxidation and hydroxylation of, 7, 7 free-radical additions to, 13, 3, 4 hydroboration of, 13, 1 hydrogenation with homogeneous catalysts, 24, 1 reactions with diazoacetic esters, 18, 3 reactions with nitrones, 36, 1 reduction by: alkoxyaluminum hydrides, 34, 1 diimides, 40, 2 organosilanes, 71, 1 Alkenes, synthesis: from amines, 11, 5 from aryl and vinyl halides, 27, 2 by Bamford-Stevens reaction, 23, 3 by Claisen and Cope rearrangements, 22, 1 by dehydrocyanation of nitriles, 31 by deoxygenation of vicinal diols, 30, 2 from α-halosulfones, 25, 1; 62, 2 by palladium-catalyzed vinylation, 27, 2 from phosphoryl-stabilized anions, 25, 2 by pyrolysis of xanthates, 12, 2 from silicon-stabilized anions, 38, 1 from tosylhydrazones, 23, 3; 39, 1 by Wittig reaction, 14, 3 Alkenyl- and alkynylaluminum reagents, 32, 2 Alkenyllithiums, formation of 39, 1 Alkoxyaluminum hydride reductions, 34, 1; 36, 3

Alkoxyphosphonium cations, nucleophilic displacements on, 29, 1 Alkylation: of allylic and benzylic carbanions, 27, 1 with amines and ammonium salts, 7, 3 of aromatic compounds, 3, 1 of esters and nitriles, 9, 4 γ-, of dianions of β-dicarbonyl compounds, 17, 2 of metallic acetylides, 5, 1 of nitrile-stabilized carbanions, 31 with organopalladium complexes, 27, 2 Alkylidenation by titanium-based reagents, 43, 1 Alkylidenesuccinic acids, synthesis and reactions of, 6, 1 Alkylidene triphenylphosphoranes, synthesis and reactions of, 14, 3 Allenylsilanes, electrophilic substitution reactions of, 37, 2 Allylboration of carbonyl compounds, 73, 1 Allyl transfer reactions, 73, 1 Allylic alcohols, synthesis: from epoxides, 29, 3 by Wittig rearrangement, 46, 2 Allylic and benzylic carbanions, heteroatom-substituted, 27, 1 Allylic hydroperoxides, in photooxygenations, 20, 2 Allylic rearrangements, transformation of glycols into 2,3-unsaturated glycosyl derivatives, 62, 4 Allylic rearrangements, trihaloacetimidate, 66, 1 π-Allylnickel complexes, 19, 2 Allylphenols, synthesis by Claisen rearrangement, 2, 1; 22, 1 Allylsilanes, electrophilic substitution reactions of, 37, 2 Aluminum alkoxides: in Meerwein-Ponndorf-Verley reduction, 2, 5 in Oppenauer oxidation, 6, 5 Amide formation by oxime rearrangement, 35, 1 α-Amidoalkylations at carbon, 14, 2

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Amination: electrophilic, of carbanions and enolates, 72, 1 of heterocyclic bases by alkali amides, 1, 4 of hydroxy compounds by Bucherer reaction, 1, 5 Amine oxides: Polonovski reaction of, 39, 2 pyrolysis of, 11, 5 Amines: from allylstannane addition to imines, 64, 1 oxidation of, 69, 1 synthesis from organoboranes, 33, 1 synthesis by reductive alkylation, 4, 3; 5, 7 synthesis by Zinin reaction, 20, 4 reactions with cyanogen bromide, 7, 4 α-Aminoacid synthesis, via Strecker Reaction, 70, 1 α-Aminoalkylation of activated olefins, 51, 2 Aminophenols from anilines, 35, 2 Anhydrides of aliphatic dibasic acids, Friedel-Crafts reaction with, 5, 5 Anion-assisted sigmatropic rearrangements, 43, 2 Anthracene homologs, synthesis of, 1, 6 Anti-Markownikoff hydration of alkenes, 13, 1 π-Arenechromium tricarbonyls, reaction with nitrile-stabilized carbanions, 31 η6 -(Arene)chromium complexes, 67, 2 Arndt-Eistert reaction, 1, 2 Aromatic aldehydes, synthesis of, 5, 6; 28, 1 Aromatic compounds, chloromethylation of, 1, 3 Aromatic fluorides, synthesis of, 5, 4 Aromatic hydrocarbons, synthesis of, 1, 6; 30, 1 Aromatic substitution by the SRN 1 reaction, 54, 1 Arsinic acids, 2, 10 Arsonic acids, 2, 10 Arylacetic acids, synthesis of, 1, 2; 22, 4 β-Arylacrylic acids, synthesis of, 1, 8

597

Arylamines, synthesis and reactions of, 1, 5 Arylation: by aryl halides, 27, 2 by diazonium salts, 11, 3; 24, 3 γ-, of dianions of β-dicarbonyl compounds, 17, 2 of nitrile-stabilized carbanions, 31 of alkenes, 11, 3; 24, 3; 27, 2 Arylglyoxals, condensation with aromatic hydrocarbons, 4, 5 Arylsulfonic acids, synthesis of, 3, 4 Aryl halides, homocoupling of, 63, 3 Aryl thiocyanates, 3, 6 Asymmetric aldol reactions using boron enolates, 51, 1 Asymmetric cyclopropanation, 57, 1 Asymmetric dihydroxylation, 66 2 Asymmetric epoxidation, 48, 1; 61, 2 Asymmetric reduction, 71, 1 Asymmetric Strecker reaction, 70, 1 Atom transfer preparation of radicals, 48, 2 Aza-Payne rearrangements, 60, 1 Azaphenanthrenes, synthesis by photocyclization, 30, 1 Azides, synthesis and rearrangement of, 3, 9 Azlactones, 3, 5 Baeyer-Villiger reaction, 9, 3; 43, 3 Bamford-Stevens reaction, 23, 3 Barbier Reaction, 58, 2 Bart reaction, 2, 10 Barton fragmentation reaction, 48, 2 B´echamp reaction, 2, 10 Beckmann rearrangement, 11, 1; 35, 1 Benzils, reduction of, 4, 5 Benzoin condensation, 4, 5 Benzoquinones: acetoxylation of, 19, 3 in Nenitzescu reaction, 20, 3 synthesis of, 4, 6 Benzylic carbanions, 27, 1; 67, 2 Biaryls, synthesis of, 2, 6; 63, 3 Bicyclobutanes, from cyclopropenes, 18, 3 Biginelli dihydropyrimidine synthesis, 63, 1 Birch reaction, 23, 1; 42, 1

598

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Bischler-Napieralski reaction, 6, 2 Bis(chloromethyl) ether, 1, 3; 19, warning Boron enolates, 51, 1 Borane reagents, for allylic transfer, 73, 1 Borohydride reduction, chiral, 52, 2 in reductive amination, 59, 1 Boyland-Sims oxidation, 35, 2 Bucherer reaction, 1, 5 Cannizzaro reaction, 2, 3 Carbanion, electrophilic amination, 72, 1 Carbenes, 13, 2; 26, 2; 28, 1 Carbene complexes in phenol and quinone synthesis, 70, 2 Carbenoid cyclopropanation, 57, 1; 58, 1 Carbohydrates, deoxy, synthesis of, 30, 2 Carbo/metallocupration, 41, 2 Carbon-carbon bond formation: by acetoacetic ester condensation, 1, 9 by acyloin condensation, 23, 2 by aldol condensation, 16; 28, 3; 46, 1;67, 1 by alkylation with amines and ammonium salts, 7, 3 by γ-alkylation and arylation, 17, 2 by allylic and benzylic carbanions, 27, 1 by amidoalkylation, 14, 2 by Cannizzaro reaction, 2, 3 by Claisen rearrangement, 2, 1; 22, 1 by Cope rearrangement, 22, 1 by cyclopropanation reaction, 13, 2; 20, 1 by Darzens condensation, 5, 10 by diazonium salt coupling, 10, 1; 11, 3; 24, 3 by Dieckmann condensation, 15, 1 by Diels-Alder reaction, 4, 1, 2; 5, 3; 32, 1 by free-radical additions to alkenes, 13, 3 by Friedel-Crafts reaction, 3, 1; 5, 5 by Knoevenagel condensation, 15, 2 by Mannich reaction, 1, 10; 7, 3 by Michael addition, 10, 3 by nitrile-stabilized carbanions, 31 by organoboranes and organoborates, 33, 1

by organocopper reagents, 19, 1; 38, 2; 41, 2 by organopalladium complexes, 27, 2 by organozinc reagents, 20, 1 by rearrangement of α-halosulfones, 25, 1; 62, 2 by Reformatsky reaction, 1, 1; 28, 3 by trivalent manganese, 49, 3 by Vilsmeier reaction, 49, 1; 56, 2 by vinylcyclopropane-cyclopentene rearrangement, 33, 2 Carbon-fluorine bond formation, 21, 1; 34, 2; 35, 3; 69, 2 Carbon-halogen bond formation, by replacement of hydroxy groups, 29, 1 Carbon-heteroatom bond formation: by free-radical chain additions to carbon-carbon multiple bonds, 13, 4 by organoboranes and organoborates, 33, 1 Carbon-nitrogen bond formation, by reductive amination, 59, 1 Carbon-phosphorus bond formation, 36, 2 Carbonyl compounds, addition of organochromium reagents, 64, 3 Carbonyl compounds, α,β-unsaturated: formation by selenoxide elimination, 44, 1 vicinal difunctionalization of, 38, 2 Carbonyl compounds, from nitro compounds, 38, 3 in the Passerini Reaction, 65, 1 oxidation with hypervalent iodine reagents, 54, 2 reactions with allylic boron compounds, 73, 1 reductive amination of, 59, 1 Carbonylation as part of intramolecular Heck reaction, 60, 2 Carboxylic acid derivatives, conversion to fluorides, 21, 1, 2; 34, 2; 35, 3 Carboxylic acids: synthesis from organoboranes, 33, 1 reaction with organolithium reagents, 18, 1 Catalytic enantioselective aldol addition, 67, 1

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Chapman rearrangement, 14, 1; 18, 2 Chloromethylation of aromatic compounds, 2, 3; 9, warning Cholanthrenes, synthesis of, 1, 6 Chromium reagents, 64, 3; 67, 2 Chugaev reaction, 12, 2 Claisen condensation, 1, 8 Claisen rearrangement, 2, 1; 22, 1 Cleavage: of benzyl-oxygen, benzyl-nitrogen, and benzyl-sulfur bonds, 7, 5 of carbon-carbon bonds by periodic acid, 2, 8 of esters via SN 2-type dealkylation, 24, 2 of non-enolizable ketones with sodium amide, 9, 1 in sensitized photooxidation, 20, 2 Clemmensen reduction, 1, 7; 22, 3 Collins reagent, 53, 1 Condensation: acetoacetic ester, 1, 9 acyloin, 4, 4; 23, 2 aldol, 16 benzoin, 4, 5 Biginelli, 63, 1 Claisen, 1, 8 Darzens, 5, 10; 31 Dieckmann, 1, 9; 6, 9; 15, 1 directed aldol, 28, 3 Knoevenagel, 1, 8; 15, 2 Stobbe, 6, 1 Thorpe-Ziegler, 15, 1; 31 Conjugate addition: of hydrogen cyanide, 25, 3 of organocopper reagents, 19, 1; 41, 2 Cope rearrangement, 22, 1; 41, 1; 43, 2 Copper-Grignard complexes, conjugate additions of, 19, 1; 41, 2 Corey-Winter reaction, 30, 2 Coumarins, synthesis of, 7, 1; 20, 3 Coupling reaction of organostannanes, 50, 1 Cuprate reagents, 19, 1; 38, 2; 41, 2 Curtius rearrangement, 3, 7, 9 Cyanation, of N-heteroaromatic compounds, 70, 1 Cyanoborohydride, in reductive aminations, 59, 1

599

Cyanoethylation, 5, 2 Cyanogen bromide, reactions with tertiary amines, 7, 4 Cyclic ketones, formation by intramolecular acylation, 2, 4; 23, 2 Cyclization: of alkyl dihalides, 19, 2 of aryl-substituted aliphatic acids, acid chlorides, and anhydrides, 2, 4; 23, 2 of α-carbonyl carbenes and carbenoids, 26, 2 cycloheptenones from α-bromoketones, 29, 2 of diesters and dinitriles, 15, 1 Fischer indole, 10, 2 intramolecular by acylation, 2, 4 intramolecular by acyloin condensation, 4, 4 intramolecular by Diels-Alder reaction, 32, 1 intramolecular by Heck reaction, 60, 2 intramolecular by Michael reaction, 47, 2 Nazarov, 45, 1 by radical reactions, 48, 2 of stilbenes, 30, 1 tandem cyclization by Heck reaction, 60, 2 Cycloaddition reactions, of cyclenones and quinones, 5, 3 cyclobutanes, synthesis of, 12, 1; 44, 2 cyclotrimerization of acetylenes, 68, 1 Diels-Alder, acetylenes and alkenes, 4, 2 Diels-Alder, imino dienophiles, 65, 2 Diels-Alder, intramolecular, 32, 1 Diels-Alder, maleic anhydride, 4, 1 [4 + 3], 51, 3 of enones, 44, 2 of ketenes, 45, 2 of nitrones and alkenes, 36, 1 Pauson-Khand, 40, 1 photochemical, 44, 2 retro-Diels-Alder reaction, 52, 1; 53, 2 [6 + 4], 49, 2 [3 + 2], 61, 1 Cyclobutanes, synthesis : from nitrile-stabilized carbanions, 31

600

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Cyclobutanes, synthesis (Continued ) by thermal cycloaddition reactions, 12, 1 Cycloheptadienes, from divinylcyclopropanes, 41, 1 polyhalo ketones, 29, 2 π-Cyclopentadienyl transition metal carbonyls, 17, 1 Cyclopentenones: annulation, 45, 1 synthesis, 40, 1; 45, 1 Cyclopropane carboxylates, from diazoacetic esters, 18, 3 Cyclopropanes: from α-diazocarbonyl compounds, 26, 2 from metal-catalyzed decomposition of diazo compounds, 57, 1 from nitrile-stabilized carbanions, 31 from tosylhydrazones, 23, 3 from unsaturated compounds, methylene iodide, and zinc-copper couple, 20, 1; 58, 1; 58, 2 Cyclopropenes, synthesis of, 18, 3 Darzens glycidic ester condensation, 5, 10; 31 DAST, 34, 2; 35, 3 Deamination of aromatic primary amines, 2, 7 Debenzylation, 7, 5; 18, 4 Decarboxylation of acids, 9, 5; 19, 4 Dehalogenation of α-haloacyl halides, 3, 3 Dehydrogenation: in synthesis of ketenes, 3, 3 in synthesis of acetylenes, 5, 1 Demjanov reaction, 11, 2 Deoxygenation of vicinal diols, 30, 2 Desoxybenzoins, conversion to benzoins, 4, 5 Dess-Martin Oxidation, 53, 1 Desulfonylation reactions, 72, 2 Desulfurization: of α-(alkylthio)nitriles, 31 in alkene synthesis, 30, 2 with Raney nickel, 12, 5 Diazo compounds, carbenoids derived from, 57, 1

Diazoacetic esters, reactions with alkenes, alkynes, heterocyclic and aromatic compounds, 18, 3; 26, 2 α-Diazocarbonyl compounds, insertion and addition reactions, 26, 2 Diazomethane: in Arndt-Eistert reaction, 1, 2 reactions with aldehydes and ketones, 8, 8 Diazonium fluoroborates, synthesis and decomposition, 5, 4 Diazonium salts: coupling with aliphatic compounds, 10, 1, 2 in deamination of aromatic primary amines, 2, 7 in Meerwein arylation reaction, 11, 3; 24, 3 in ring closure reactions, 9, 7 in synthesis of biaryls and aryl quinones, 2, 6 Dieckmann condensation, 1, 9; 15, 1 for synthesis of tetrahydrothiophenes, 6, 9 Diels-Alder reaction: intramolecular, 32, 1 retro-Diels-Alder reaction, 52, 1; 53, 2 with alkynyl and alkenyl dienophiles, 4, 2 with cyclenones and quinones, 5, 3 with imines, 65, 2 with maleic anhydride, 4, 1 Dihydrodiols, 63, 2 Dihydropyrimidine synthesis, 63, 1 Dihydroxylation of alkenes, asymmetric, 66, 2 Diimide, 40, 2 Diketones: pyrolysis of diaryl, 1, 6 reduction by acid in organic solvents, 22, 3 synthesis by acylation of ketones, 8, 3 synthesis by alkylation of β-diketone anions, 17, 2 Dimethyl sulfide, in oxidation reactions, 39, 3 Dimethyl sulfoxide, in oxidation reactions, 39, 3

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Diols: deoxygenation of, 30, 2 oxidation of, 2, 8 Dioxetanes, 20, 2 Dioxiranes, 61, 2; 69, 1 Dioxygenases, 63, 2 Divinyl-aziridines, -cyclopropanes, -oxiranes, and -thiiranes, rearrangements of, 41, 1 Doebner reaction, 1, 8 Eastwood reaction, 30, 2 Elbs reaction, 1, 6; 35, 2 Electrophilic amination, 72, 1 fluorination, 69, 2 Enamines, reaction with quinones, 20, 3 Enantioselective: aldol reactions, 67, 1 allylation and crotylation, 73, 1 Ene reaction, in photosensitized oxygenation, 20, 2 Enolates: Fluorination of, 69, 2 α-Hydroxylation of, 62, 1 in directed aldol reactions, 28, 3; 46, 1; 51, 1 Enone cycloadditions, 44, 2 Enzymatic reduction, 52, 2 Enzymatic resolution, 37, 1 Epoxidation: of alkenes, 61, 2 of allylic alcohols, 48, 1 with organic peracids, 7, 7 Epoxide isomerizations, 29, 3 Epoxide formation, 61, 2 migration, 60, 1 Esters: acylation with acid chlorides, 1, 9 alkylation of, 9, 4 alkylidenation of, 43, 1 cleavage via SN 2-type dealkylation, 24, 2 dimerization, 23, 2 glycidic, synthesis of, 5, 10 hydrolysis, catalyzed by pig liver esterase, 37, 1 β-hydroxy, synthesis of, 1, 1; 22, 4 β-keto, synthesis of, 15, 1

601

reaction with organolithium reagents, 18, 1 reduction of, 8, 1; 71, 1 synthesis from diazoacetic esters, 18, 3 synthesis by Mitsunobu reaction, 42, 2 Ethers, synthesis by Mitsunobu reaction, 42, 2 Exhaustive methylation, Hofmann, 11, 5 Favorskii rearrangement, 11, 4 Ferrocenes, 17, 1 Fischer carbene complexes, 70, 2 Fischer indole cyclization, 10, 2 Fluorinating agents, electrophilic, 69, 2 Fluorination of aliphatic compounds, 2, 2; 21, 1, 2; 34, 2; 35, 3; 69, 2 of carbonyl compounds, 69, 2 of heterocycles, 69, 2 Fluorination: by DAST, 35, 3 by N-F reagents, 69, 2 by sulfur tetrafluoride, 21, 1; 34, 2 Formylation: by hydroformylation, 56, 1 of alkylphenols, 28, 1 of aromatic hydrocarbons, 5, 6 of aromatic compounds, 49, 1 of non-aromatic compounds, 56, 2 Free radical additions: to alkenes and alkynes to form carbon-heteroatom bonds, 13, 4 to alkenes to form carbon-carbon bonds, 13, 3 Freidel-Crafts catalysts, in nucleoside synthesis, 55, 1 Friedel-Crafts reaction, 2, 4; 3, 1; 5, 5; 18, 1 Friedl¨ander synthesis of quinolines, 28, 2 Fries reaction, 1, 11 Gattermann aldehyde synthesis, 9, 2 Gattermann-Koch reaction, 5, 6 Germanes, addition to alkenes and alkynes, 13, 4 Glycals, fluorination of, 69, 2 transformation in glycosyl derivatives, 62, 4

602

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Glycosides, synthesis of, 64, 2 Glycosylating agents, 68, 2 Glycosylation on polymer supports, 68, 2 Glycosylation, with sulfoxides and sulfinates, 64, 2 Glycidic esters, synthesis and reactions of, 5, 10 Gomberg-Bachmann reaction, 2, 6; 9, 7 Grundmann synthesis of aldehydes, 8, 5 Halides, displacement reactions of, 22, 2; 27, 2 Halide-metal exchange, 58, 2 Halides, synthesis: from alcohols, 34, 2 by chloromethylation, 1, 3 from organoboranes, 33, 1 from primary and secondary alcohols, 29, 1 Haller-Bauer reaction, 9, 1 Halocarbenes, synthesis and reactions of, 13, 2 Halocyclopropanes, reactions of, 13, 2 Halogen-metal interconversion reactions, 6, 7 α-Haloketones, rearrangement of, 11, 4 α-Halosulfones, synthesis and reactions of, 25, 1; 62, 2 Heck reaction, intramolecular, 60, 2 Helicenes, synthesis by photocyclization, 30, 1 Heterocyclic aromatic systems, lithiation of, 26, 1 Heterocyclic bases, amination of, 1, 4 in nucleosides, 55, 1 Heterodienophiles, 53, 2 Hilbert-Johnson method, 55, 1 Hoesch reaction, 5, 9 Hofmann elimination reaction, 11, 5; 18, 4 Hofmann reaction of amides, 3, 7, 9 Homocouplings mediated by Cu, Ni, and Pd, 63, 3 Homogeneous hydrogenation catalysts, 24, 1 Hunsdiecker reaction, 9, 5; 19, 4 Hydration of alkenes, dienes, and alkynes, 13, 1 Hydrazoic acid, reactions and generation of, 3, 8

Hydroboration, 13, 1 Hydrocyanation of conjugated carbonyl compounds, 25, 3 Hydroformylation, 56, 1 Hydrogenation catalysts, homogeneous, 24, 1 Hydrogenation of esters, with copper chromite and Raney nickel, 8, 1 Hydrohalogenation, 13, 4 Hydroxyaldehydes, aromatic, 28, 1 α-Hydroxyalkylation of activated olefins, 51, 2 α-Hydroxyketones,: rearrangement, 62, 3 synthesis of, 23, 2 Hydroxylation: of enolates, 62, 1 of ethylenic compounds with organic peracids, 7, 7 Hypervalent iodine reagents, 54, 2; 57, 2 Imidates, rearrangement of, 14, 1 Imines, additions of allyl, allenyl, propargyl stannanes, 64, 1 additions of cyanide, 70, 1 as dienophiles, 65, 2 synthesis, 70, 1 Iminium ions, 39, 2; 65, 2 Imino Diels-Alder reactions, 65, 2 Indoles, by Nenitzescu reaction, 20, 3 by reaction with TosMIC, 57, 3 Ionic hydrogenation, 71, 1 Isocyanides, in the Passerini reaction, 65, 1 sulfonylmethyl, reactions of, 57, 3 Isoquinolines, synthesis of, 6, 2, 3, 4; 20, 3 Jacobsen reaction, 1, 12 Japp-Klingemann reaction, 10, 2 Katsuki-Sharpless epoxidation, 48, 1 Ketene cycloadditions, 45, 2 Ketenes and ketene dimers, synthesis of, 3, 3; 45, 2 α-Ketol rearrangement, 62, 3 Ketones: acylation of, 8, 3

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

alkylidenation of, 43, 1 Baeyer-Villiger oxidation of, 9, 3; 43, 3 cleavage of non-enolizable, 9, 1 comparison of synthetic methods, 18, 1 conversion to amides, 3, 8; 11, 1 conversion to fluorides, 34, 2; 35, 3 cyclic, synthesis of, 2, 4; 23, 2 cyclization of divinyl ketones, 45, 1 reaction with diazomethane, 8, 8 reduction to aliphatic compounds, 4, 8 reduction by: alkoxyaluminum hydrides, 34, 1 organosilanes, 71, 1 reduction in anhydrous organic solvents, 22, 3 synthesis by oxidation of alcohols, 6, 5; 39, 3 synthesis from acid chlorides and organo-metallic compounds, 8, 2; 18, 1 synthesis from organoboranes, 33, 1 synthesis from organolithium reagents and carboxylic acids, 18, 1 synthesis from α,β-unsaturated carbonyl compounds and metals in liquid ammonia, 23, 1 Kindler modification of Willgerodt reaction, 3, 2 Knoevenagel condensation, 1, 8; 15, 2; 57, 3 Koch-Haaf reaction, 17, 3 Kornblum oxidation, 39, 3 Kostaneki synthesis of chromanes, flavones, and isoflavones, 8, 3 β-Lactams, synthesis of, 9, 6; 26, 2 β-Lactones, synthesis and reactions of, 8, 7 Leuckart reaction, 5, 7 Lithiation: of allylic and benzylic systems, 27, 1 by halogen-metal exchange, 6, 7 heteroatom facilitated, 26, 1; 47, 1 of heterocyclic and olefinic compounds, 26, 1 Lithioorganocuprates, 19, 1; 22, 2; 41, 2 Lithium aluminum hydride reductions, 6, 2 chirally modified, 52, 2 Lossen rearrangement, 3, 7, 9

603

Mannich reaction, 1, 10; 7, 3 Meerwein arylation reaction, 11, 3; 24, 3 Meerwein-Ponndorf-Verley reduction, 2, 5 Mercury hydride method to prepare radicals, 48, 2 Metalations with organolithium compounds, 8, 6; 26, 1; 27, 1 Methylenation of carbonyl groups, 43, 1 Methylenecyclopropane, in cycloaddition reactions, 61, 1 Methylene-transfer reactions, 18, 3; 20, 1; 58, 1 Michael reaction, 10, 3; 15, 1, 2; 19, 1; 20, 3; 46, 1; 47, 2 Microbiological oxygenations, 63, 2 Mitsunobu reaction, 42, 2 Moffatt oxidation, 39, 3; 53, 1 Morita-Baylis-Hillman reaction, 51, 2 Nazarov cyclization, 45, 1 Nef reaction, 38, 3 Nenitzescu reaction, 20, 3 Nitriles: formation from oximes, 35, 2 synthesis from organoboranes, 33, 1 α,β-unsaturated: by elimination of selenoxides, 44, 1 Nitrile-stabilized carbanions: alkylation and arylation of, 31 Nitroamines, 20, 4 Nitro compounds, conversion to carbonyl compounds, 38, 3 Nitro compounds, synthesis of, 12, 3 Nitrone-olefin cycloadditions, 36, 1 Nitrosation, 2, 6; 7, 6 Nucleosides, synthesis of, 55, 1 Olefin formation, by reductive elimination of β-hydroxysulfones, 72, 2 Olefins, hydroformylation of, 56, 1 Oligomerization of 1,3-dienes, 19, 2 Oligosaccharide synthesis on polymer support, 68, 2 Oppenauer oxidation, 6, 5 Organoboranes : formation of carbon-carbon and carbon-heteroatom bonds from, 33, 1

604

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Organoboranes (Continued ) in allylation of carbonyl compounds, 73, 1 isomerization and oxidation of, 13, 1 reaction with anions of α-chloronitriles, 31, 1 Organochromium reagents: addition to carbonyl compounds, 64, 3; 67, 2 addition to imines, 67, 2 Organohypervalent iodine reagents, 54, 2; 57, 2 Organometallic compounds: of aluminum, 25, 3 of chromium, 64, 3; 67, 2 of copper, 19, 1; 22, 2; 38, 2; 41, 2 of lithium, 6, 7; 8, 6; 18, 1; 27, 1 of magnesium, zinc, and cadmium, 8, 2; of palladium, 27, 2 of silicon, 37, 2 of tin, 50, 1; 64, 1 of zinc, 1, 1; 20, 1; 22, 4; 58, 2 Organosilicon hydride reductions, 71, 1 Osmium tetroxide asymmetric dihydroxylation, 66, 2 Overman rearrangement of allylic imidates, 66, 1 Oxidation: by dioxiranes, 61, 2; 69, 1 of alcohols and polyhydroxy compounds, 6, 5; 39, 3; 53, 1 of aldehydes and ketones, Baeyer-Villiger reaction, 9, 3; 43, 3 of amines, phenols, aminophenols, diamines, hydroquinones, and halophenols, 4, 6; 35, 2 of enolates and silyl enol ethers, 62, 1 of α-glycols, α-amino alcohols, and polyhydroxy compounds by periodic acid, 2, 8 with hypervalent iodine reagents, 54, 2 of organoboranes, 13, 1 of phenolic compounds, 57, 2 with peracids, 7, 7 by photooxygenation, 20, 2 with selenium dioxide, 5, 8; 24, 4 Oxidative decarboxylation, 19, 4

Oximes, formation by nitrosation, 7, 6 Oxochromium(VI)-amine complexes, 53, 1 Oxo process, 56, 1 Oxygenation of arenes by dioxygenases, 63, 2 Palladium-catalyzed vinylic substitution, 27, 2 Palladium-catalyzed coupling of organostannanes, 50, 1 Palladium intermediates in Heck reactions, 60, 2 Passerini Reaction, 65, 1 Pauson-Khand reaction to prepare cyclopentenones, 40, 1 Payne rearrangement, 60, 1 Pechmann reaction, 7, 1 Peptides, synthesis of, 3, 5; 12, 4 Peracids, epoxidation and hydroxylation with, 7, 7 in Baeyer-Villiger oxidation, 9, 3; 43, 3 Periodic acid oxidation, 2, 8 Perkin reaction, 1, 8 Persulfate oxidation, 35, 2 Peterson olefination, 38, 1 Phenanthrenes, synthesis by photocyclization, 30, 1 Phenols, dihydric from phenols, 35, 2 oxidation of, 57, 2 synthesis from Fischer carbene complexes, 70, 2 Phosphinic acids, synthesis of, 6, 6 Phosphonic acids, synthesis of, 6, 6 Phosphonium salts: halide synthesis, use in, 29, 1 synthesis and reactions of, 14, 3 Phosphorus compounds, addition to carbonyl group, 6, 6; 14, 3; 25, 2; 36, 2 addition reactions at imine carbon, 36, 2 Phosphoryl-stabilized anions, 25, 2 Photochemical cycloadditions, 44, 2 Photocyclization of stilbenes, 30, 1 Photooxygenation of olefins, 20, 2 Photosensitizers, 20, 2 Pictet-Spengler reaction, 6, 3 Pig liver esterase, 37, 1 Polonovski reaction, 39, 2

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Polyalkylbenzenes, in Jacobsen reaction, 1, 12 Polycyclic aromatic compounds, synthesis by photocyclization of stilbenes, 30, 1 Polyhalo ketones, reductive dehalogenation of, 29, 2 Pomeranz-Fritsch reaction, 6, 4 Pr´evost reaction, 9, 5 Pschorr synthesis, 2, 6; 9, 7 Pummerer reaction, 40, 3 Pyrazolines, intermediates in diazoacetic ester reactions, 18, 3 Pyridinium chlorochromate, 53, 1 Pyrolysis: of amine oxides, phosphates, and acyl derivatives, 11, 5 of ketones and diketones, 1, 6 for synthesis of ketenes, 3, 3 of xanthates, 12, 2 Quaternary ammonium N-F reagents, 69, 2 salts, rearrangements of, 18, 4 Quinolines, synthesis of, by Friedl¨ander synthesis, 28, 2 by Skraup synthesis, 7, 2 Quinones: acetoxylation of, 19, 3 diene additions to, 5, 3 synthesis of, 4, 6 synthesis from Fischer carbene complexes, 70, 2 in synthesis of 5-hydroxyindoles, 20, 3 Ramberg-B¨acklund rearrangement, 25, 1; 62, 2 Radical formation and cyclization, 48, 2 Rearrangements: allylic trihaloacetamidate, 66, 1 anion-assisted sigmatropic, 43, 2 Beckmann, 11, 1; 35, 1 Chapman, 14, 1; 18, 2 Claisen, 2, 1; 22, 1 Cope, 22, 1; 41, 1, 43, 2 Curtius, 3, 7, 9 divinylcyclopropane, 41, 1 Favorskii, 11, 4

605

Lossen, 3, 7, 9 Ramberg-B¨acklund, 25, 1; 62, 2 Smiles, 18, 2 Sommelet-Hauser, 18, 4 Stevens, 18, 4 [2,3] Wittig, 46, 2 vinylcyclopropane-cyclopentene, 33, 2 Reduction: of acid chlorides to aldehydes, 4, 7; 8, 5 of aromatic compounds, 42, 1 of benzils, 4, 5 of ketones, enantioselective, 52, 2 Clemmensen, 1, 7; 22, 3 desulfurization, 12, 5 with diimide, 40, 2 by dissolving metal, 42, 1 by homogeneous hydrogenation catalysts, 24, 1 by hydrogenation of esters with copper chromite and Raney nickel, 8, 1 hydrogenolysis of benzyl groups, 7, 5 by lithium aluminum hydride, 6, 10 by Meerwein-Ponndorf-Verley reaction, 2, 5 chiral, 52, 2 by metal alkoxyaluminum hydrides, 34, 1; 36, 3 by organosilanes, 71, 1 of mono- and polynitroarenes, 20, 4 of olefins by diimide, 40, 2 of α,β-unsaturated carbonyl compounds, 23, 1 by samarium(II) iodide, 46, 3 by Wolff-Kishner reaction, 4, 8 Reductive alkylation, synthesis of amines, 4, 3; 5, 7 Reductive amination of carbonyl compounds, 59, 1; 71, 1 Reductive cyanation, 57, 3 Redutive desulfonylation, 72, 2 Reductive desulfurization of thiol esters, 8, 5 Reformatsky reaction, 1, 1; 22, 4 Reimer-Tiemann reaction, 13, 2; 28, 1 Reissert reaction, 70, 1 Resolution of alcohols, 2, 9 Retro-Diels-Alder reaction, 52, 1; 53, 2 Ritter reaction, 17, 3

606

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Rosenmund reaction for synthesis of arsonic acids, 2, 10 Rosenmund reduction, 4, 7 Samarium(II) iodide, 46, 3 Sandmeyer reaction, 2, 7 Schiemann reaction, 5, 4 Schmidt reaction, 3, 8, 9 Selenium dioxide oxidation, 5, 8; 24, 4 Seleno-Pummerer reaction, 40, 3 Selenoxide elimination, 44, 1 Shapiro reaction, 23, 3; 39, 1 Silanes: addition to olefins and acetylenes, 13, 4 electrophilic substitution reactions, 37, 2 oxidation of, 69, 1 reduction with, 71, 1 Sila-Pummerer reaction, 40, 3 Silyl carbanions, 38, 1 Silyl enol ether, α-hydroxylation, 62 1 Simmons-Smith reaction, 20, 1; 58, 1 Simonini reaction, 9, 5 Singlet oxygen, 20, 2 Skraup synthesis, 7, 2; 28, 2 Smiles rearrangement, 18, 2 Sommelet-Hauser rearrangement, 18, 4 SRN 1 reactions of aromatic systems, 54, 1 Sommelet reaction, 8, 4 Stevens rearrangement, 18, 4 Stetter reaction of aldehydes with olefins, 40, 4 Strecker reaction, catalytic asymmetric, 70, 1 Stilbenes, photocyclization of, 30, 1 Stille reaction, 50, 1 Stobbe condensation, 6, 1 Substitution reactions using organocopper reagents, 22, 2; 41, 2 Sugars, synthesis by glycosylation with sulfoxides and sulfinates, 64, 2 Sulfide reduction of nitroarenes, 20, 4 Sulfonation of aromatic hydrocarbons and aryl halides, 3, 4 Swern oxidation, 39, 3; 53, 1 Tetrahydroisoquinolines, synthesis of, 6, 3 Tetrahydrothiophenes, synthesis of, 6, 9 Thia-Payne rearrangement, 60, 1

Thiazoles, synthesis of, 6, 8 Thiele-Winter acetoxylation of quinones, 19, 3 Thiocarbonates, synthesis of, 17, 3 Thiocyanation of aromatic amines, phenols, and polynuclear hydrocarbons, 3, 6 Thiophenes, synthesis of, 6, 9 Thorpe-Ziegler condensation, 15, 1; 31 Tiemann reaction, 3, 9 Tiffeneau-Demjanov reaction, 11, 2 Tin(II) enolates, 46, 1 Tin hydride method to prepare radicals, 48, 2 Tipson-Cohen reaction, 30, 2 Tosylhydrazones, 23, 3; 39, 1 Tosylmethyl isocyanide (TosMIC), 57, 3 Transmetallation reactions, 58, 2 Tricarbonyl(η6 -arene)chromium complexes, 67, 2 Trihaloacetimidate, allylic rearrangements, 66, 1 Trimethylenemethane, [3 + 2] cycloaddtion of, 61, 1 Trimerization, co-, acetylenic compounds, 68, 1 Ullmann reaction: homocoupling mediated by Cu, Ni, and Pd, 63, 3 in synthesis of diphenylamines, 14, 1 in synthesis of unsymmetrical biaryls, 2, 6 Unsaturated compounds, synthesis with alkenyl- and alkynylaluminum reagents, 32, 2 Vilsmeier reaction, 49, 1; 56, 2 Vinylcyclopropanes, rearrangement to cyclopentenes, 33, 2 Vinyllithiums, from sulfonylhydrazones, 39, 1 Vinylsilanes, electrophilic substitution reactions of, 37, 2 Vinyl substitution, catalyzed by palladium complexes, 27, 2 von Braun cyanogen bromide reaction, 7, 4 Vorbr¨uggen reaction, 55, 1

CHAPTER AND TOPIC INDEX, VOLUMES 1–73

Willgerodt reaction, 3, 2 Wittig reaction, 14, 3; 31 [2,3]-Wittig rearrangement, 46, 2 Wolff-Kishner reaction, 4, 8

Ylides: in Stevens rearrangement, 18, 4 in Wittig reaction, structure and properties, 14, 3

Xanthates, synthesis and pyrolysis of, 12, 2

Zinc-copper couple, 20, 1; 58, 1, 2 Zinin reduction of nitroarenes, 20, 4

607