Compendium of Organic Synthetic Methods, Volume 9

Compendium of Organic Synthetic Methods

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Compendium of Organic Synthetic Methods Volume 9 MICHAEL B. SMITH DEPARTMENT OF CHEMISTRY THE UNIVERSITY OF CONNECTICUT STORRS, CONNECTICUT

A Wiley-Interscience Publication

JOHN WILEY & SONS, INC. New York

Chichester

Weinheim

Brisbane

Singapore

Toronto

Cover illustration was adapted from "Disconnect By the Numbers: A Beginner's Guide to Synthesis" by M. B. Smith. Journal of Chemical Education, 1990, 67, 848-856.

This book is printed on acid-free paper. © Copyright © 2001 by John Wiley & Sons, 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 Sections 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, 222 Rosewood Drive, Davers, MA 01923, (978) 750-8400, fax (978) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail: [email protected]. For ordering and customer service, call 1-800-CALL-WILEY. Library of Congress Cataloging Card Number: 71-162800 ISBN 0-471-14579-3 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1

CONTENTS PREFACE ABBREVIATIONS INDEX, MONOFUNCTIONALCOMPOUNDS INDEX, DIFUNCTIONAL COMPOUNDS INTRODUCTION 1 2 3 4 5 6 7 8 9

10 11 12 13 14 15 16

PREPARATION OF ALKYNES PREPARATION OF ACID DERIVATIVES PREPARATION OF ALCOHOLS PREPARATON OF ALDEHYDES PREPARATION OF ALKYLS, METHYLENESAND ARYLS PREPARATION OF AMIDES PREPARATION OF AMINES PREPARATION OF ESTERS PREPARATION OF ETHERS, EPOXIDES AND THIOETHERS PREPARATION OF HALIDES AND SULFONATES PREPARATION OF HYDRIDES PREPARATION OF KETONES PREPARATION OF NITRILES PREPARATION OF ALKENES PREPARATION OF OXIDES PREPARATION OF DIFUNCTIONAL COMPOUNDS AUTHOR INDEX

vii IX

xiii xiv xv 1 5 11 48 58 100 117 140 156

171 176 183 208

212 227 235 391

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PREFACE Since the original volume in this series by Ian and Shuyen Harrison, the goal of the Compendium of Organic Synthetic Methods was to facilitate the search for functional group transformations in the original literrature of Organic Chemistry. In Volume 2, difunctional compounds were added and this compilation was continued by Louis Hegedus and Leroy Wade for Voume 3 of the series. Wade became the author for Volume 4 and continued with Volume 5. I began editing the series with Volume 6, where I introduced an author index for the first time and added a new chapter (Chapter 15, Oxides). Volume 7 introduced Sections 378 (Oxides-Alkynes) through Section 390 (Oxides-Oxides). The Compendium is a handy desktop reference that will remain a valuable tool to the working Organic chemist, allowing a "quick check" of the literature. It also allows one to "browse" for new reactions and transformations that may be of interest. The body of Organic literature is very large and the Compendium is a focused and highly representative review of the literature and is offered in that context. Compendium of Organic Synthetic Methods, Volume 9 contains both functional group transformations and carbon-carbon bond forming reactions from the literature appearing in the years 1993, 1994 and 1995. The classification schemes used for volumes 6-8 have been continued. Difunctional compounds appear in Chapter 16. The experienced user of the Compendium will require no special insructions for the use of Volume 9. Author citations and the Author Index have been continued as in Volumes 6-8. Every effort has been made to keep the manuscript error free. Where there are errors I take full responsibility. If there are questions or comments, the reader is encouraged to contact me directly at the address, phone, fax, or Email addresses given below. As I have througout my writing career, I thank my wife Sarah and my son Steven who have shown unfailing patience and devotion during this work. I also thank Darla Henderson, the editor of this volume. Michael B. Smith Department of Chemistry University of Connecticut 55 N. Eagleville Road Storrs, Connecticut 06269-3060 Voice phone: (860)-486-2881 Fax: (860)-486-2981 Email: [email protected]

VII

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ABBREVIATIONS O Ac

Acetyl

acac AIBN aq.

Acetylacetonate azo-to-isobutyronitrile Aqueous 9-Borabicyclo[3.3.1 ]nonylboryl

9-BBN BER BINAP Bn Bz

9-Borabicyclo[3.3.1]nonane Borohydride exchange resin 2/?,35-2,2'-&w-(diphenylphosphino)-l,l'-binapthyl benzyl benzoyl

BOC

r-Butoxycarbonyl

bpy (Bipy) Bu CAM CAN ccat.

2,2'-Bipyridyl n-Butyl Carboxamidomethyl Ceric ammonium nitrate cycloCatalytic

Cbz

Carbobenzyloxy

Chirald COD COT Cp CSA CTAB

2S,3R-(+)-4-dimethylamino-1,2-diphenyl-3-methylbutan-2-ol 1,5-Cyclooctadienyl 1,3,5-cyclooctatrienyl Cyclopentadienyl Camphorsulfonic acid cetyltrimethylammonium bromide

Cy (c-C6H j !)

Cyclohexyl

°C DABCO dba DBE DBN DBU DCC

Temperature in Degrees Centigrade 1,4-Diazobicyclo[2.2.2]octane dibenzylidene acetone 1,2-Dibromoethane l,8-Diazabicyclo[5.4.0]undec-7-ene l,5-Diazabicyclo[4.3.0]non-5-ene 1,3-Dicyclohexylcarbodiimide

O "hx^\ *\ Ot-Bu

-CH2CH2CH2CF (NH)2Ce(NO3)g O

JL

•*t s OCH 2 Ph

BrCH2CH2Br

c-C6H13-N=C=N-c-C6H13

ix

ABBREVIATIONS DCE DDQ % de DBA DEAD Dibal-H Diphos (dppe) Diphos-4 (dppb) DMAP DMA DME

1,2-Dichloroethane 2, 3-Dichloro-5,6-dicyano-l,4-benzoquinone % Diasteromeric excess Diethylamine Diethylazodicarboxylate Diisobutylaluminum hydride l,2-£zs-(Diphenylphosphino)ethane l,4-fe/5-(Diphenylphosphino)butane 4-Dimethylaminopyridine Dimethylacetamide Dimethoxyethane

DMF

MAr-Dimethylformaniide

dmp dpm dppb dppe dppf dppp dvb e~ % ee EE Et EDA EDTA FMN fod Fp FVP h hv 1,5-HD HMPA HMPT iPr LICA (LIPCA) LDA LHMDS LTMP MABR MAD mCPBA Me MEM Mes

C1CH2CH2C1

HN(CH2CH3)2 EtO2C-N=NCO2Et (Me2CHCH2)2AlH Ph2PCH2CH2PPh2 Ph2P(CH2)4PPh2

MeOCH2CH2OMe

O II '^ bis-[ 1 ,3-Di(/?-methoxyphenyl)- 1 ,3-propanedionato] dipivaloylmethanato l,4-fe-(Diphenylphosphino)butane Ph2P(CH2)4PPh2 l,2-to-(Diphenylphosphino)ethane Ph2PCH2CH2PPh2 ^w-(Diphenylphosphino)ferrocene l,3-to-(Diphenylphosphino)propane Ph2P(CH2)3PPh2 Divinylbenzene Electrolysis % Enantiomeric excess 1-Ethoxyethyl EtO(Me)HCOEthyl -CH2CH3 Ethylenediamine H2NCH2CH2NH2 Ethylenediaminetetraacetic acid Flavin mononucleotide fn'5'-(6,6,7,7,8,8,8)-Heptafluoro-2,2-dimethyl-3,5-octanedionate Cyclopentadienyl-few-carbonyl iron Flash Vacuum Pyrolysis hour (hours) Irradiation with light 1,5-Hexadienyl Hexamethylphosphoramide (Me3N)3P=O Hexamethylphosphorous triamide (Me^N)^? Isopropyl -CH(CH3)2 Lithium cyclohexylisopropylamide Lithium diisopropylamide LiN(iPr)2 Lithium hexamethyl disilazide LiN(SiMe3)2 Lithium 2,2,6,6-tetramethylpiperidide Methylaluminum i»w-(4-bromo-2,6-di-ferf-butylphenoxide) &w-(2,6-di-?-butyl-4-methylphenoxy)methyl aluminum m^to-Chloroperoxybenzoic acid Methyl -CH3 p-Methoxyethoxymethyl MeOCH2CH2OCH2Mesityl 2,4,6-tri-Me-C6H2

ABBREVIATIONS

xi

MOM Ms MS MTM NAD NADP Napth NBD NBS NCS NIS Ni(R) NMP Oxone

Methoxymethyl Methanesulfonyl Molecular Sieves (3 A or 4 A) Methylthiomethyl Nicotinamide adenine dinucleotide Sodium triphosphopyridine nucleotide Napthyl (C1QH8) Norbornadiene Af-Bromosuccinimide Af-Chlorosuccinimide Af-Iodosuccinimide Raney nickel N-Methyl-2-pyrrolidinone 2 KHSO5«KHSO4«K2SO4

MeOCH2CH3SO2-

(P)

Polymeric backbone

PCC PDC PEG

Pyridinium chlorochromate Pyridinium dichromate Polyethylene glycol

Ph

Phenyl

PhH PhMe Phth pic

Benzene Toluene Phthaloyl 2-Pyridinecarboxylate

Pip

Piperidine

PMP

4-methoxyphenyl

Pr

n-Propyl

-CH2CH2CH3

Py

Pyridine

/ N

quant. Red-Al sBu sBuLi Siamyl TADDOL TASF TBAF TBDMS TBHP (f-BuOOH) r-Bu TEBA TEMPO

Quantitative yield [(MeOCH2CH2O)2AlH2]Na sec-Butyl CH3CH2CH(CH3) sec-Butyllithium CH3CH2CH(Li)CH3 Diisoamyl (CH3)2CHCH(CH3)a,a,a',a'-tetraaryl-4,5-dimethoxy-1,3-dioxolane rm-(Diethylamino)sulfonium difluorotrimethyl silicate Tetrabutylammonium fluoride n-Bu4N+F f-Butyldimethylsilyl ?-BuMe2Si f-Butylhydroperoxide Me3COOH tert-Butyl -C(CH3)3 Triethylbenzylammonium Bn(CH3)3N+ Tetramethylpiperdinyloxy free radical

CH3SCH2-

H—N\

^_y

xii

ABBREVIATIONS

TFA TFAA Tf (OTf) THF THP TMEDA TMG TMS TMP TPAP Tol Tr TRIS Ts(Tos)

Trifluoroacetic acid Trifluoroacetic anhydride Triflate Tetrahydrofuran Tetrahydropyran Tetramethylethylenediamine 1,1,3,3-Tetramethylguanidine Trimethylsilyl 2,2,6,6-Tetramethylpiperidine tetra-n-Propylammonium perruthenate Tolyl Trityl Triisopropylphenylsulfonyl Tosyl = p-Toluenesulfonyl

))))))))

Sonication

Xc

Chiral auxiliary

CF3COOH (CF3CO)2O -SO2CF3(-OSO2CF3)

-Si(CH3)3

4-C6H4CH3 -CPh3 4-MeC6H4

INDEX, MONOFUNCTIONAL COMPOUNDS Sections—heavy type Pages—light type Blanks in the table correspond to sections for which no additional examples were found in the literature

PROTECTION

Carboxylic acids Alcohols, phenols Aldehydes Amides Amines Ketones

Sect.

Pg.

30A 4SA 60A 90A 105A 180A

9 42 55 115 137 206

PREPARATION OF [ FROM)

^ Alkynes

#

31 11

Aldehydes Alkyls, methylenes, aryls Amides

17 5

18 6

19 6

32 11

33 12

34 13

47 48

48 48

49 49

50 50

63 60

64 60

65 61

61 58 76 100

77 100

Esters

106 140

Ethers, epxoides

121 156

107 140

137 171

Halides, sulfonates

23 7 36 25

80 102

78 101

52 51

166 183

167 184

99 129

113 146

114 148

111 145

123 156

124 158

128 159 140 172

Nitriles

183 208

184 208 199 217

Alkenes

196 212

197 216

198 217

Miscellaneous

211 227

212 227

213 227

171 191

172 192

186 209 200 219

129 160

142 172 157 177

201 220

'* 10 2

12 3

14 3

15 3

25 7

27 8

29 8

30 9

44 39

45 41

59 54

70 55

74 72

75 99

40 29 55 52 70 65

100 130 115 149 130 161 145 173

158 178 173 193

41 30

159 179

160 179

174 193

175 195

71 70

202 220

203 220

204 221

205 221

217 228

218 228

219 228

220 232

43 39 58 53

72 71 87 112

88 113

89 113

90 113

101 131

102 131

103 132

104 132

105 133

116 150

117 151

118 153

119 154

120 154

131 161

132 161

146 173

147 174 162 181

176 196

190 209

188 209

42 30 57 53

85 111

98 129

109 144

170 191

69 65

97 120

108 142

169 189

54 52

83 110

96 119

168 186

53 51

82 108

153 176

Hydrides (RH)

39 26

81 102

94 118

138 171

24 7

38 26

68 64

93 117


'*"V

^

Amines

Ketones

^^

1 1

Carboxylic acid derivatives Alcohols, phenols

?j

^J

134 162 149 175 163 182

177 198

179 202

180 204 195 211

207 223 222 232

15« 175 165 182

192 210

221 232

135 169

223 233

209 223

210 225

234 233

225 233

XIII

INDEX, DIFUNCTIONAL COMPOUNDS Sections—heavy type Pages—light type Blanks in the table correspond to sections for which no additional examples were found in the literature

XIV

382

383

384

385

386

387

383

383

384

38S

386

386

INTRODUCTION Relationship between Volume 9 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 9 presents about 1200 examples of published reactions for the preparation of monofunctional compounds, updating the 10650 in Volumes 1-8. Volume 9 contains about 800 examples of reactions which prepare of difunctional compounds with various functional groups. Reviews have long been a feature of this series and Volume 9 adds almost 90 pertinent reviews in the various sections. Volume 9 contains approximately 1000 fewer entries than Volume 8 for an identical three-year period, primarily for difunctional compunds. Interestingly, there are about 500 fewer citations from the most cited journal (Tetrahedron Letters) than in the previous edition. Whether this represents a trend in the literature or an inadvertent selectivity on my part is unknown, but there has been a clear increase in biochemical and total synthesis papers which may account for this. Chapters 1-14 continue as in Volumes 1-8, as does Chapter 15, introduced in Volume 6. Difunctional compounds appear in Chapter 16, as in Volumes 6 and 7. The sections on oxides as part of difunctional compounds, introduced in Volume 7, continues in Chapter 16 of Volumes 8 and 9 with Sections 378 (Oxides-Alkynes) through Section 390 (Oxides-Oxides). Following Chapter 16 is a complete alphabetical listing of all authors (last name, initials). The authors for each citation appear below the reaction. The principle author is indicated by underlining (i.e., Kwon, T.W.; Smith. M. B.). as in Volumes 7 and 8. Classification and Organization of Reactions Forming Monofunctional Compounds. Chemical transformations are classified according to the reacting functional group of the starting material and the functional group formed. Those reactions that give products with the same functional group form a chapter. The reactions in each chapter are further classified into sections on the basis of the functional group of the starting material. Within each section, reactions are loosely arranged in ascending order of year cited (1993-1995), although an effort has been made to put similar reactions together when possible. Review articles are collected at the end of each appropriate section. The classification is unaffected by allylic, vinylic, or acetylenic unsaturation appearing in both starting material and product, or by increases or decreases in the length of carbon chains; for example, the reactions f-BuOH - f-BuCOOH, PhCH2OH - PhCOOH, and PhCH=CHCH2OH PhCH=CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Conjugate reduction and alkylation of unsaturated

xv

xvi

INTRODUCTION

ketones, aldehydes, esters, acids, and nitriles have been placed in Sections 74D and 74E (Alkyls from Alkenes), respectively. The terms hydrides, alkyls, and aryls classify compounds containing reacting hydrogens, alkyl groups, and aryl groups, respectively; for example, RCH2-H — RCH2COOH (carboxylic acids from hydrides), RMe - RCOOH (carboxylic acids from alkyls), RPh — RCOOH (carboxylic acids from aryls). Note the distinction between R2CO -» R2CH2 (methylenes from ketones) and RCOR' — RH (hydrides from ketones). Alkylations involving additions across double bonds are found in Section 74 (alkyls, methylenes, and aryls from alkenes). The following examples illustrate the classfication of some potentially confusing cases: RCH=CHCOOH RCH=CH2 ArH ArH RCHO RCH=CHCHO RCHO R2CH2 RCH2COR RCH=CH2

— RCH=CH2 - RCH=CHCOOH —• ArCOOH — ArOAc - RH - RCH=CH2 - RCH3 — R2CO - R2CHCOR - RCH2CH3

RBr + HC=CH - RCH=CR ROH + RCOOH — RCOOR RCH=CHCHO - RCH2CH2CHO RCH=CHCN - RCH2CH2CN

Hydrides from carboxylic acids Carboxylic acids from hydrides Carboxylic acids from hydrides Esters from hydrides Hydrides from aldehydes Hydrides from aldehydes Alkyls from aldehydes Ketones from methylenes Ketones from ketones Alkyls from alkenes (Hydrogenation of Alkenes) Alkynes from halides; also alkynes from alkynes Esters from alcohols; also esters from carboxylic acids Alkyls from alkenes (Conjugate Reduction) Alkyls from alkenes (Conjugate Rduction)

How to Use the Book to Locate Examples of the Preparation of Protection of Monofunctional Compounds. Examples of the preparation of one functional group from another are found in the monofunctional index on p. x, which lists the corresponding section and page. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of this index. Section 1 gives examples of the reactions of alkynes that form new alkynes; Section 16 gives reactions of alkynes that form carboxylic acids; and Section 31 gives reactions of alkynes that form alcohols. Examples of alkylation, dealkylation, homologation, isomerization, and transposition are found in Sections 1,17, 33, and so on, lying close to a diagonal of the index. These sections correspond to such topics as the preparation of alkynes from alkynes; carboxylic acids from carboxylic acids; and

INTRODUCTION

xvii

alcohols, thiols, and phenols from alcohols, thiols, and phenols. Alkylations that involve conjugate additions across a double bond are found in Section 74E (Alkyls, Methylenes, and Aryls from Alkenes). Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Section 199 (Alkenes from Aldehydes) and Section 207 (Alkenes frorm Ketones). The aldol condensation can be found in the chapters on difunctional compounds in Section 324 (Alcohol, Thiol-Aldehyde) and in Section 330 (Alcohol, Thiol-Ketone). Examples of the protection of alkynes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and alkenes are also indexed on p. xvii. Section (designated with an A: 15A, 30A, etc.) with "protecting group: reactions are located at the end of pertinent chapters. Some pairs of functional groups such as alcohol, ester; carboxylic acid, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. When a member of these groups is the desired product or starting material, the other member should also be consulted in the text. The original literature must be used to determine the generality of reactions, although this is occasionally stated in the citation. This is only done in cases where such generality is stated clearly in the original citation. A reaction given in this book for a primary aliphatic substrate may also be applicable to tertiary or aromatic compounds. This book provides very limited experimental conditions or precautions and the reader is referred to the original literature before attempting a reaction. In no instance should a citation in this book be taken as a complete experimental procedure. Failure to refer to the original literature prior to beginning laboratory work could be hazardous. The original papers usually yield a further set of references to previous work. Papers that appear after those publications can usually be found by consulting Chemical Abstracts and the Science Citation Index. Classification and Organization of Reactions Forming Difunctional Compounds. This chapter considers all possible difunctional compounds formed from the groups acetylene, carboxylic acid, alcohol, thiol, aldehyde, amide, amine, ester, ether, epoxide, thioether, halide, ketone, nitrile, and alkene. Reactions that form difunctional compounds are classified into sections on the basis of two functional grups in the product that are pertinent to the reaction. The relative positions of the groups do not affect the classification. Thus preparations of 1,2-amino-alcohols, 1,3-amino-alcohols, and 1,4amino-alcohols are included in a single section (Section 326, AlcoholAmine). Difunctional compounds that have an oxide as the second group are found in the appropriate section (Sections 278-290). The nitroketone product of oxidation of a nitroalcohol is found in Section 386 (Ketone-Oxide). Conversion of an oxide to another functional grup is generally found in the "Miscellaneous" section of the sections concerning monofunctional com-

xviii

INTRODUCTION

pounds. Conversion of a nitroalkane to an amine, for example is found in Section 105 (Amines from Miscellaneous Compounds). The following examples illustrate applications of this classification system: Difunctional Product ROC—OCR RCH(OH)COOH RCH=CHOMe RCHF2 RCH(Br)CH2F RCH(OAc)CH2OH RCH(OH)CO2Me RCH=CHCH2CO2Me RCH=CHOAc RCH(OMe)CH2SO2CH2CH2OH RSO2CH2CH2OH

Section Title Alkyne-Alkyne Carboxylic acid-Alcohol Ether-Alkene Halide-Halide Halide-Halide Alcohol-Ester Alcohol-Ester Ester-Alkene Ester-Alkene Alcohol-Ether Alcohol-Oxide

How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on p. xi gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol, ThiolEster) contains examples of the preparation of hydroxyesters; Section 323 (Alcohol, Thiol-Alcohol, Thiol) contains examples of the preparation of diols. Some preparations of alkene and acetylenic compounds from alkene and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, the transformation RCH=CHBr - RCH=CHCOOH could be considered as preparing carboxylic acids from halides (Section 25, monofunctional compounds) or preparing a carboxylic acid-alkene (Section 322, difunctional compounds). The choice usually depends on the focus of the particular paper where this reaction was found. In such cases both sections should be consulted. Reactions applicable to both aldehyde and ketone starting materials are in many cases illustrated by an example that uses only one of them. Likewise, many citations for reactions found in the Aldehyde-X sections, will include examples that could be placed in the Ketone-X section. Again the choice is dictated by the paper where the reaction was found. Many literature preparations of difunctional compounds are extensions of the methods applicable to monofunctional compounds. As an example, the reaction RCI — ROM might be used for the preparation of diols from an appropriate dichloro compund. Such methods are difficult to categorize and may be found in either the monofunctional or difunctional sections, depending on the focus of the original paper. The user should bear in mind that the pairs of functional groups alcohol, ester; carboxylic acids, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. Compounds of the type

INTRODUCTION

xix

RCH(OAc)CH2OAc (ester-ester) would thus be of interest to anyone preparing the diol RCH(OH)CH2OH (alcohol-alcohol). Sources of Literature Citations. I thought it would be useful for a reader of this Compendium to see the distribution of citations used to this book (i.e., which journals have the most new synthetic methodology). As seen in the accompanying graph, Tetrahedron Letters and Journal of Organic Chemistry account for roughly 60% of all the citations in Volume 9. This book was not edited to favor one journal, category or type of article over another. Undoubtedly, my own personal preferences are part of the selection but I believe that this compilation is an accurate represention of new synthetic methods that appear in the literature for this period. Therefore, I believe the accompanying graph reflects those journals where new synthetic methodology is located. I should point out that the category "18 other journals" includes: Accts. Chem. Res.; Acta Chem. Scand.; Angew. Chem. Int. Ed. Engl.; Bull. Chim. Soc. Belg.; Bull. Chim. Soc. Fr.; Can. J. Chem.; Chem. Ber; Gazz. Chim. Ital.; Heterocycles; J. Chem. Soc.; J. Met. Chem.; J. Indian Chem. Soc; LiebigsAnn. Chem.; Org. Prep. Proceed Int.; Reel. Trav. Chim., Pays-Bas; and Tetrahedron Asymmetry. In addition, nine more journals were examined but no references were recorded.

xx

INTRODUCTION

Citations

1 . ^H

u

Journal

Compendium of Organic Synthetic Methods

This page intentionally left blank

CHAPTER 1 PREPARATION OF ALKYNES

SECTION 1: ALKYNES FROM ALKYNES

•SiMePh2

Me2CHCH2I, THF Smlz-Sm

^

^

SiMePh2

80%

Murakami. M.: Hayashi, M.; Ito. Y. Svnlett. 1994, 179 (CH2)4OAc

Ph

P h—

— Ph , toluene

5% Mo(CO)6, HO°C, 20°C AcO(H2Q4 4-chlorophenol AcO(H2C)4 g()% Kaneta, N.; Hikichi, K.; Asaka, S.; Uemura, M.; Mori. M. Chem. Lett., 1995, 1055 REVIEW:

"Palladium And/Or Copper-Mediated Cross-Coupling Reactions Between 1-Alkynes And Vinyl, Aryl, 1-Alkynyl, 1,2-Propadienyl, Propargyl And Allylic Halides Or Related Compounds. A Review," Rossi. R.: Carpita, A.; Bellina, F. Org. Prep. Proceed. Int., 1995, 27, 129 SECTION 2: ALKYNES FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES SECTION 3: ALKYNES FROM ALCOHOLS AND THIOLS NO ADDITIONAL EXAMPLES SECTION 4: ALKYNES FROM ALDEHYDES NO ADDITIONAL EXAMPLES

Compendium of Organic Synthetic Methods, Vol 9

SECTION 5:

Section 10

ALKYNES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES

SECTION 6:

ALKYNES FROM AMIDES NO ADDITIONAL EXAMPLES

SECTION 7:

ALKYNES FROM AMINES NO ADDITIONAL EXAMPLES

SECTION 8:

ALKYNES FROM ESTERS NO ADDITIONAL EXAMPLES

SECTION 9:

ALKYNES FROM ETHERS, EPOXIDES AND TfflOETHERS NO ADDITIONAL EXAMPLES

SECTION 10:

ALKYNES FROM HALIDES AND SULFONATES HO

~

Pd/C, PPh3, Cul, DME K2CO3

\/

Br Bleicher, L.: Cosford. N.D.P. Svnlett. 1995, 1115

\ 98%

Cul, Pd(PPh3>4, NEt3 , PhMe I 95%

Bates. R.W.: Gabel, C.J.; Ji, J. Tetrahedron Lett., 1994, 35, 6993

//

NO2

Section 15

Alkynes from Misc.

SECTION 11:

ALKYNES FROM HYDRIDES

For examples of the reaction ROCH -» ROC-OCR1, see section 300 (Alkyne-Alkyne). NO ADDITIONAL EXAMPLES SECTION 12:

ALKYNES FROM KETONES Yb, THF, HMPA

*-

Ph

Ph

-10°C, 20 min 67% Taniguchi, Y.; Fujii, N.; Makioka, Y.; Takai, K.; Fujiwara, Y. Chem. Lett., 1993, 1165

TMSC(Li)N2,THF

-*• -78°C -» reflux Miwa, K.; Aovama. T.: Shioiri. T. Svnlett. 1994, 107 J. 11

Ph

=

Me

58%

i.YJ.1/

SECTION 13:

ALKYNES FROM NITRILES NO ADDITIONAL EXAMPLES

SECTION 14:

ALKYNES FROM ALKENES

Bl.

OSiPh2r-Bu

OSiPh2r-Bu NaHMDS , THF -100°C Grandjean, D.; Pale, P.; Chuche, J. Tetrahedron Lett., 1994, 35, 3529 SECTION 15:

ALKYNES FROM MISCELLANEOUS COMPOUNDS FVP (750°C)

'r-Bu

82% Aitken. R.A.: Atherton, J.I. J. Chem. Soc., Perkin Trans. 1., 1994, 1281 From arylCO derivatives: Aitken. R.A.: Horsburgh, C.E.R.; McCreadie, J.G.; Seth, S. J. Chem. Soc., Perkin Trans. 1., 1994, 1727

4

SECTION ISA:

Compendium of Organic Synthetic Methods, Vol 9

PROTECTION OF ALKYNES NO ADDITIONAL EXAMPLES

Section ISA

Section 17

Acids from Acids

5

CHAPTER 2 PREPARATION OF ACID DERIVATIVES

SECTION 16:

ACID DERIVATIVES FROM ALKYNES NO ADDITIONAL EXAMPLES

SECTION 17:

ACID DERIVATIVES FROM ACID DERIVATIVES

CO2H

BuLi , THF-HMPA

OMe MeO

MeO

(10 : 1) 82% Kusumoto. T.: Ichikawa, S.; Asaka, K.; Sato, K.; Hiyama, T. Tetrahedron Lett., 1995, 36, 1071

microwave , 4 min OAc

Villemin. P.: Labiad, B.; Loupy, A. Synth. Commun., 1993, 23, 419

Compendium of Organic Synthetic Methods, Vol 9

SECTION 18:

Section 22

ACID DERIVATIVES FROM ALCOHOLS AND TfflOLS O 2 , PbCOAc)2-3 H2Q, Pd-C, In

NaOH , H20,150°C Akada. M.: Nakano, S.; Sugiyama, T.; Tchitoh, K.; Nakao, H.; Akita, M.: Moro-Oka. Y. Bull. Chem. Soc. Jpn., 1993, 66, 1511 l.PhKOAc^.AcOH rt,8h 2.H20 92% Kirihara, M.; Yokoyama, S.; Kakuda, H.; Momose. T. Tetrahedron Lett., 1995, 36, 6907

SECTION 19: ACID DERIVATIVES FROM ALDEHYDES H^.HCC^H PhCHO — Dodd. R.H.: Le Hyaric, M. Synthesis, 1993, 295 ,CHO

-

PhCO2H

93%

NaClO2, aq. MeCN

10°C -> rt

Phf

93% Babu, B.R.; Balasubramanian. K.K. Org. Prep. Proceed. Int., 1994, 26,123 NaNs-MnOySiCU, CH;£12,0°C PhCHO

A

Elmorsv. S.S. Tetrahedron Lett., 1995, 36, 1341 SECTION 20:

ACID DERIVATIVES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES

SECTION 21: ACID DERIVATIVES FROM AMIDES NO ADDITIONAL EXAMPLES SECTION 22: ACID DERIVATIVES FROM AMINES NO ADDITIONAL EXAMPLES

Section 25

Acids from Halides

SECTION 23: ACID DERIVATIVES FROM ESTERS Other reactions useful for the hydrolysis of esters may be found in Section 30A (Protection of Carboxylic Acids).

Rawal. V.H.: Zhong, H.M. Tetrahedron Lett., 1994, 35, 4947 1. 2 eq. KOH/Aliquat, microwave PhCO2Me

PhCO2H 2.HC1 Loupy. A.: Pigeon, P.; Ramdani, M.; Jacquault, P. Synth. Commun., 1994, 24, 159 CO (3 atm), 8% PPh3 96h,rt 'OCHO 2% Pd2(dba)3CHCl3, toluene

^^ ^\ *" PIT ^^ C02H 92% (E only)

Yamamnto. A. Bull. Chem. Soc. Jpn., 1995, 68, 433

SECTION 24:

-

ACID DERIVATIVES FROM ETHERS, EPOXIDES AND THIOETHERS

—.__ O

1. 10% [Bi(mandelate)2]2O DMSO , 80°C , 30 min, air 60%

V/ V

2. H3O+ Zevaco, T.; DufSach, E.; Postel. M. Tetrahedron Lett., 1993, 34, 2601 OSiMe3

XCO2H

AgBrO3 , A1C13 , MeCN reHux, 0.35h 02N

Firouzabadi. H.: Mohammadpoor-Baltork, I. Synth. Commun., 1994, 24, 1065

SECTION 25:

ACID DERIVATIVES FROM HALIDES AND SULFONATES Mel

CO2 , H2 ,150°C, Id

MeCC^H

Ni(cod)2 + Co2(CO)8 Fukuoka. A.: Gotoh, N.; Kobayashi, N.; Hirano, M.; Komiva. S. Chem. Lett., 1995, 567

Compendium of Organic Synthetic Methods, Vol 9

Section 29

REVIEW: "Preparation OfThiol Acids, Thiol Esters And Amides By Reactions Of Carbonyl Sulfides With Grignard Reagents," Katritzky. A.R.: Moutou, J.-L.; Yang, Z. Org. Prep. Proceed. Int., 1995, 27, 361 SECTION 26: ACID DERIVATIVES FROM HYDRIDES NO ADDITIONAL EXAMPLES SECTION 27: ACID DERIVATIVES FROM KETONES

Na£O3-3/2 H2O2,60°C

3h Yang. D.T.C.: Cao, Y.H.; Kabalka, G.W. Synth. Commun., 1995, 25, 3695 SECTION 28: ACID DERIVATIVES FROM NITRILES NO ADDITIONAL EXAMPLES SECTION 29: ACID DERIVATIVES FROM ALKENES ,

Fe(CO)5, KOH, CO (1 atm) H2O/iPrOH, 55°C, 4d

Me (96 : 4) 45% Brunet. J.-J.: Neibecker, D.; Srivastava, R.S. Tetrahedron Lett., 1993, 34, 2759 HCO2H, CO (6.8 atm) , DME Pd(OAc)2 - dppb , 150°C , 16h

\_

I

86%

El AH. B.: Alper, H. J. Org. Chem., 1993, 58, 3595 D.

\

t==

HCOOH,6.8atmCO 10% Pd/C , dppb , DME 150°C,ld

(76 : El Ali. B.: Vasapollo, G.; Alper. H. J. Org. Chem., 1993, 58, 4739

ph.

24) 65%

Section 30A

C6Hi3 y

Protection of Acids

cat. OsO4, Jones reagent

^

85%

C6H13—C02H

acetone, rt Henry, J.R.; Weinreh. S.M. 7 Org. Chem., 1993, 58, 4745 Pd/C , dppb , PPh3 , CO HCOOH.DME 60% Vasapollo, G.; Somasunderam, A.; El Ali, B.; Alper. H. Tetrahedron Lett., 1994, 35, 6203

PhCH=CH2

O2 , 2% Co(acac)3 , THF -------^ 7

PhCO2H

C ld

°° ' (86 Reetz. M.T.: Tollner, K. Tetrahedron Lett., 1995, 36, 9461 SECTION 30:

PhIO2

PhCHO

14)99%

ACID DERIVATIVES FROM MISCELLANEOUS COMPOUNDS 1. 0.1% Na2[PdCl4l , CO , H2O Na2C03 , 40°C , 6.5h -^

PhCOOH

+

2. H3O Grushin, V.V.; Alper. H. J. Org. Chem., 1993, 58, 4794 SECTION 30A:

+

PROTECTION OF CARBOXYLIC ACID DERIVATIVES

Ph

5 TBAF»xH2O SBnSH PhCOOH

O 82% Ueki. M.: Aoki, H.; Katoh, T. Tetrahedron Lett., 1993, 34, 2783

acidic A12O3 , 7 min microwave , CH2C12 , it O Varma. R.S.: Chatterjee, A.K.; Varma, M. Tetrahedron Lett., 1993, 34, 4603

71%

10

Compendium of Organic Synthetic Methods, Vol 9

Section 30A

H(

caL DMAP

• rt > 6

I2 , cyclohexane , rt

75% Cossv. J.: Albouy, A.; Scheloske, M.; Gomez Pardo, D. Tetrahedron Lett., 1994, 35, 1539

DCC , 0.1 DMAP, THF O2H 93%

quant \

"""

^

/

/

Mpeoc group

1% TFA in CH2C12 , 5 min , rt Bernatowicz. M.S.: Chao, H.-G.; Matsueda, G.R. Tetrahedron Lett., 1994, 55,1651 CuCl 2 ,O 2 ,aq.DMF ^

Ph

Ph—CC^H

~ Ph 45% Ram. R.N.: Singh, L. Tetrahedron Lett., 1995, 36, 5401 CO2Bn

l.NBS,(BzO) 2 ,CCl 4 ,heat

2. H2O * Anson. M.S.: Montana, J.G. Synlett, 1994, 219

'

83%

REVIEW: "Recent Developments in Chemical Deprotection of Ester Functional Groups," Salomon, C.J.; Mata, E.G.; Mascaretti, O.A. Tetrahedron, 1993, 49, 3691

Other reactions useful for the protection of carboxylic acids are included in Section 107 (Esters from Carboxylic Acids and Acid Halides) and Section 23 (Carboxylic Acids from Esters).

Section 32

CHAPTER

Alcohols from Acids

11

3

PREPARATION

OF

ALCOHOLS

SECTION 31: ALCOHOLS AND THIOLS FROM ALKYNES 1. BH3»NEt2Ph C8Hn 3. BnBr 4.H 2 0 2 ,OHReddy, Ch.K.; Periasamv. M. Tetrahedron, 1993, 49, 8897 SECTION 32:

OH

62%

ALCOHOLS AND THIOLS FROM ACID DERIVATIVES H

BuLi, CeCl3, THF

OH

16h , -78°C

'

*"

)

Bu

Ahn, Y.; Cohen. T. Tetrahedron Lett., 1994, 35, 203 NaBH 4 -I 2 ,THF 94% reHux / f\ H NH2 H NH2 McKennon, M.J.; Mevers. A.I.: Drauz. K.: Schwann, M. J. Org. Chem., 1993, 58, 3568

Zn(BH4)2 , THF , reflux Ph—COOH -- Ph—CH2OH Narasimhan. S.: Madhavan, S.; Prasad, K.G. J. Org. Chem., 1995, 60, 5314

2.NaBH 4 ,MeOH

90% Barton, D.H.R.; Castagnino. E.: Jaszberenyi, J.Cs. Tetrahedron Lett., 1994, 35, 6057

12

Compendium of Organic Synthetic Methods, Vol 9

Section 33

Sml2-H20 , 1 min *-

PhCH2OH

Kamnchi. Y .: Kudo, T. Chem. Lett., 1993, 1495 H2 (100 atm) , DME , 160°C -^ 5% Ru/Al2O3—Mo(CO)6

Ci4H29COOH

C14H29CH2OH

95%

He, D.-H.; Wakasa, N.; Fuchikami. T. Tetrahedron Lett., 1995, 36, 1059 l.NaBH 4 ,H 2 O 2. 10%aq.HCl

85%

Sharma. R.: Voymov, G.H.; Ovaska. T.V.: Marquez, V.E. Synlett, 1995, 839 SECTION 33:

ALCOHOLS AND THIOLS FROM ALCOHOLS AND THIOLS OH

Lawesson's reagent, toluene *" fi I

reflux

^^**""*^ \ I >

67%

Nishio. T. J. Chem. Soc., Perkin Trans. 1., 1993, 1113 BF3OEt2,THF -

\

\

/

/

^-

QTT

\

0°C,lh

Kahalka. G.W.: Reddy, N.K.; Narayana, C. Tetrahedron Lett., 1993, 34, 7667 4SmI 2 ,8KOH

\_?

\

/)

UH

MeoH

/

v

/

\_y

*• \

)

v

\_y

OH + /

10% Kamochi. Y.: Kudo, T. Tetrahedron Lett., 1994, 35, 4169

Geotrichium candidum immobilized OH with a water-adsorbent r-adsorl polymer . ph hexane 89%ee,R (56 Nakamura. K.: Inoue, Y.; Ohno, A. Tetrahedron Lett., 1994, 35, 4375

)

OH

73%

H

, :

44)

Section 34A

Reduction of Aldehydes to Alcohols

13

SECTION 34: ALCOHOLS AND THIOLS FROM ALDEHYDES The following reaction types are included in this section: A. Reductions of Aldehydes to Alcohols B. Alkylation of Aldehydes, forming Alcohols. Coupling of Aldehydes to form Diols is found in Section 323 (Alcohol-Alcohol).

MeO

k

ft

CHO

H2O2, EtOH , 50°C MgSO 4 ,MeReO 3 ,ld

*- MeO

Yamazaki. S. Chem. Lett., 1995, 127 SECTION 34A:

REDUCTIONS OF ALDEHYDES TO ALCOHOLS Na2Te , NMP , PhH

Ph—CHO

OH

*-

80°C, 0.8h Suzuki. H.: Nakamura, T. 7. Org. Chem., 1993, 58, 241

Ph

/ '

rq% Dy '°

/ \ © © 1. PhCHO,THF,3h PhCH OH + ' V-AlHEt2 Na ' \ / 50% Yoon. N.M.: Ahn, J.H.; An, D.K.; Shon, Y.S. J. Org. Chem., 1993, 58, 1941 ,CHO

PhCHO 50%

1. (iPrO)2TiCiyBnEt3NBH4, CH2C12 -20°C 2. aq. K£O3

90% Ravikumar, K.S.; Baskaran, S.: Chandrasekaran. S. 7. Org. Chem., 1993, 58, 5981

BfyCN-NH^Hv CHO

-

EtOH

v ..

f

87%

Das. M.K.: Maiti, P.K.; Bhaumik, A. Bull. Chem. Soc. Jpn., 1993, 66, 810 = LiInH4 92% Yamada, M.; Tanaka, K.; Araki, S.; Butsugan. Y. Tetrahedron Lett., 1995, 36, 3169

14

Compendium of Organic Synthetic Methods, Vol 9

MeQ

Section 34B

Me

, SiO2, rt MeO

<^

^

CHO

CH2C12,

Id "OH

81% Figadere. B.: Chaboche, C.; Franck, X.; Peyrat, J.-F. J. Org. Chetn., 1995, 60, 7138

REVIEW: "P-Hydroxy Diisopinocampheylborane As A Mild, Chemoselective Reducing Agent For Aldehydes," Cha. J.S.: Kim, E.J.; Kwon, O.O.; Kwon, S.Y.; Seo, W.W.; Chang, S.W. Org. Prep. Proceed. Int., 1995, 27, 541

SECTION 34B:

ALKYLATION OF ALDEHYDES, FORMING ALCOHOLS ASYMMETRIC ALKYLATIONS Et2Zn

OH

THO B

\i(OiPr)2 88% / (83%ee) Tf Knochel. P.: Brieden, W.; Rozema, M.; Eisenberg, C. Tetrahedron Lett., 1993, 34, 5881

PhCHO

1.10% R(+)2-binaphthol, Ti(OiPr)4 CH2C12 ^

I

, NaHCO3

71%

(93%ee , R) Keck. G.E.: Geraci, L.S. Tetrahedron Lett., 1993, 34, 7827 R-BINOL/Ti(OiPr)4 , MS 4A , TFA

H

PhCHO -20°C , 14h , 95% (96% ee) Keck. G.E.: Krishnamurthy, D.; Grier, M.C. J. Org. Chetn., 1993, 58, 6543

Section 36

Alcohols from Amides

15

CC1;£HO, R-BINOL-TiCl2 MS 4A, 0°C , CH2C12

(62

CCb

:

38) 78%

[>95%ee]

CCb

[>95%ee]

Mikami. K.: Yajima, T.; Terada, M.; Uchimaru, T. Tetrahedron Lett., 1993, 34, 7591 • SnBu3

— *,CH2C12

OH

PhCHO 20% (binol)TiC!2 , rt , 2d • ee,S) Costa, AX-.; Piazza, M.G.; Tagliavini. E.: Trombini, C.; Umani-Ronchi. A. /. Am. Chem. Soc., 1993, 115, 7001

j

[ Ti(OiPr)4/l,l'-bi-2-naphthol, MS4A1 I CH2C12, reflux j

PhCHO

*-

-78°C,10min 2.

^^^ SnBu3 , -20°C , 70h

88% (95%ee,R) Keck. G.E.: Tarbet, K.H.; Geraci, L.S. /. Am. Chem. Soc., 1993, 115, 8467

1. Et2Zn , 25°C, 10%

UO#*\,UH

OH

PhCHO 2. 2N HCl

ph.

80% ee

Mehler, T.; Martens. L: Wallbaum, S. Synth. Commun., 1993, 23, 2691

!.ZnEt2, 10% V^N PhCHO

>••«• CPh2OH

OH -

2.2NHC1,-20°C

100% ee Wallbaum, S.; Martens. J. Tetrahedron Asymmetry, 1993, 4, 637 With a chiral oxazoline additive, 60% ee Allen, J.V.; Frost, C.G.; Williams. J.M.J. Tetrahedron Asymmetry, 1993, 4, 649

16

Compendium of Organic Synthetic Methods, Vol 9

Section 34B

l.BuLi

2. PhCHO

)H

N — 3.ZnEt2

4.2NHC1

98% ee, S Behnen, W.; Mehler, T.; Martens. T. Tetrahedron Asymmetry, 1993, 4,1413 Et2Zn , toluene, hexane

PhCHO

OH Ph

Me

| s Et

*-

OTBS Ph

95%(85%ee,R)

Et

de Vries, E.F.J.; Brussee. J.: Kruse, C.G.; van der Gen, A. Tetrahedron Asymmetry, 1993, 4, 1987 ZnEt 2 ,5% iPr2NH

PhCHO

5%

OH Ph

i

quant. (46% ee, R) Sheng Jian, L.; Yaozhong. J.: Aiqiao, M.; Guishu, Y. /. Chem. Soc., Perkin Trans. L, 1993, 885 Et2Zn . PhMe, it PhCHO

.0.

Hn

H

Ph' 90% (96%ee,R)

Cho. B.T.: Kim, N. Tetrahedron Lett., 1994, 35, 4115

HO Me2Zn, PhMe, 0°C, Ti(0,-Bu)4,8%-NHTf with Ti(OiPr)4 - 80% yield, 0% ee Nowotng, S.; Vettel, S.; Knochel. P. Tetrahedron Lett., 1994, 35, 4539

76%(93%e e)

Section 36

Alcohols from Amides

17

BuaSn PhCHO, (R)-Binol 0.5 Ti(OiPr)4 , -20°C

"*, Ph (14

>99% ee Keck. G.E.: Krishnamurthy, D.; Chen, X. Tetrahedron Lett., 1994, 35, 8323 )H

PhCHO

ZnEt? , hexane/toluene , 10% chiral ligand -20°C , 28h

72% (80% ee) Andr6s, J.M.; Martfnez, M.A.; Pedrosa. R.t Perez-Encabo, A. Tetrahedron Asymmetry, 1994, 5, 67

ZnEt2 , 5% chiral ligand PhCHO 16h

OH

s~

70% (68% ee , R) Ishizaki, M.; Fujita, K.; Shimamoto, M.; Hoshino. O. Tetrahedron Asymmetry, 1994, 5, 411

Et2Zn PhCHO Me. / \

N

OH P

v_/

Ph«**^ ** SH 94% (ioo% ee) Kang. J.: Lee, J.W.; Kim, J.I. J. Chem. Soc. Chem. Commun., 1994, 2009

Ph Watanabe, M.: Soai. K. .7. Chem. Soc., Perkin Trans. L, 1994, 3125

quant. (93% ee)

18

Compendium of Organic Synthetic Methods, Vol 9

Section 34B

Et2Zn, 22°C PhCHO

^ 10% /

j

Pn

\»'"CH(Mes)OLi

^—*^ N

70-90% (86% ee, S)

Bn

Stingl, K.; Martens. J. Ucbigs Ann. Chem., 1994, 491 PhCHO

Et2Zn, chiral ferrocene catalyst toluene

X^x/

85%(55%ee,R)

Fukuzawa. S.: Tsudzuki, K. Tetrahedron Asymmetry, 1995, 6, 1039

/

K, \/N-B

*—'

'

\( ^"

"""-"I

. SnBr,

/

PhCHO CH2C12 , -78°C 93% (79% ee)

Kobavashi. S.: Nishio, K. Tetrahedron Lett., 1995, 36, 6729 OH , CH2CJ2 ,

58%(87%ee) 20% Zr-BINOL derivative Bedeschi, P.; Casolari, S.; Costa, A.L.; Tagliavini. E.: Umani-Ronchi, A. Tetrahedron Lett., 1995, 36, 7897 1. chiral Ti complex, ether

X

2. TFA, THE

OTMS 97% (80% ee)

Singer, R.A.; Carreira. E.M. /. Am. Chem. Soc., 1995, 117, 12360 NON-ASYMMETRIC ALKYLATIONS Sn(CH2CH=CH2)4, D-arabinose, rt Ph—CHO 5% Sc(OT03 , aq. MeCN Hachiya, I.; Kobayashi, S. J. Org. Chem., 1993, 58, 6958

OH

Section 36

Alcohols from Amides

19

PhCHO, Et3Zn , THF cat. Pd(PPh3>4, rt, 3h

OH

o Yasui, K.; Goto, Y.; Yajima, T.; Taniseki, Y.; Fugami, K.; Tanaka, A.; Tamaru. Y. Tetrahedron Lett., 1993, 34, 7619 diethyl ether, -50°C PhCHO

-

98%

(<1:>99 symanti) Wissing, E.; Havennith, R.W.A.; Boersma, J.; Smeets, W.J.J.; Spek, A.L.; van Koten. G. J. Org. Chem., 1993, 58, 4228 BuCHO

.Ph ^

PhTi(OiPr)3 , -40°C 2MAPH,PhLi,-78°C

(3.3 (1

_ „„

: :

.Ph ^

1) 60% 10.8)60%

MAPH = ArOAr, Ar = 2,5-diphenylphenyl Maruoka, K.; Saito, S.; Concepcion, A.B.; Yamamoto. H. /. Am. Chem. Soc., 1993, 115, 1183

C7H,5—CHO

l

, THF/aq. HC1 C7H15X

20°C, Ih

>99% Yanagisawa, A.; Inoue, H.; Morodome, M.; Yamamoto. H. J. Am. Chem. Soc., 1993, 115, 10356 , CH2C12,25°C PhCHO

-

5% Ir(CO)(PPh3)2ClO4,30h Nuss. J.M.: Rennels, R.A. Chem. Lett., 1993, 197 1. ^^XX1 ,SnCl2»2H2O PhCHO Nal.DMF 2. 30% NH4F, H2O Imai. T.: Nishida, S. Synthesis, 1993, 395

1

^

83%

20

Compendium of Organic Synthetic Methods, Vol 9

1. Bu3SnSiMe3, THF, 3h,

Section 34B

rt

OH

2. H30+

82% Bhatt, R.K.; Ye, J.; Falck. J.R. Tetrahedron Lett., 1994, 35, 4081

^

)H I

^^

PhCHO 5% Yb(OTf)3

85% Aspinall, H.C.; Browning, A.F.; Greeves. N.: Ravenscroft, P. Tetrahedron Lett., 1994, 35, 4639 9H

,DMF,rrt

, Ih 85% Hashimoto, Y.; Kagoshima, H.; Saigo. K. Tetrahedron Lett., 1994, 35, 4805 OTIPS TIPS( OTTPS

CgH nCHO, Me2AlCl, hexane

>

OTIPS

-78°C, 17h SMe

'* \ OH Masaya, K.; Tanino, K.; Kuwaiima. I. Tetrahedron Lett., 1994, 35, 7965 chirality transfer ene reaction

„„„, , nonf , 90% (>98% ee)

-OMe BU3S

f

i

••

l.BuLi,THF,-78 2. PhCHO

-OMe 90% (70:30 de) Colombo. L.: DiGiacomo, M.; Brusotti, G.; Delougu, G. Tetrahedron Lett., 1994, 35, 2063 OT-J

1. Li (powder), naphthalene 2. Li (powder) , naphthalene 3. PhCHO Guijarro, D.; Yus. M. Tetrahedron Lett., 1994, 35, 2965

/ Et-/ \

Ph

Section 36

Alcohols from Amides

21

SiMe3 l.Ga.KI.LiCl PhCHO, THF, reflux

2. Br (91 Han, Y.; Huang. Y.-Z. Tetrahedron Lett., 1994, 35, 9433

C6Hi3CHO

-HO^ J

+

HO^X^C3H7

BuSnCl 3 ,CHCl 3 ,0°C

(98 Mivaki. H.: Yamamura, K. Chem. Lett., 1994, 897

2) 86%

:

1. ^\/Br , 0.5 CuCl, THF, rt

QH

PhCHO 1.5SnCl 2 «2H 2 O,ld 2. 30% aq. Imai. T.X: Nishida, S. /. Chem. Soc. Chem. Commun., 1994, 273

Ph EtCHO , Zn , aq. NH4C1, THF

_

'Cl

lit

OH

98% (73:27) Sjoholm. R.: Rairama, R.; Ahonen, M. /. Chem. Soc. Chem. Commun., 1994, 1217 cat. Pd(PPh3)4 , PhCHO Et2Zn , THF , reflux Clayden, J.; Julia. M. J. Chem. Soc. Chem. Commun., 1994, 1905

OH

22

Compendium of Organic Synthetic Methods, Vol 9

Section 34B

2.2 Et2Zn, C9H19CHO 77%

Clavden. J.: Julia, M. /. Chem. Soc. Chem. Commun., 1994, 2261 CHO

PhCH2SiMe3 , hv , MeCN

y^-^ OSiMe

Mg(ClO4)2,6.5h

\\ Fukuzumi. S.: Okamoto, T.; Otera. J. /. Am. Chem. Soc., 1994, 116, 5503 Cl

l.Ba* 2. PhCHO ,THF, -78°C

(97 (>99:1 E:Z) Yanagisawa, A.; Habaue, S.; Yasue, K.; Yamamoto. H. /. Am. Chem. Soc., 1994, 116, 6130

OH CHO

'SnBu3 InCl3 , acetone, 5h, -78°C -* rt 90%

(98:2 anti:syn) Marshall. J.A.: Hinkle, K.W. J. Org. Chem., 1995, 60, 1920 ,Sid3

1. PhCHO,DMF,0°C 2. H20 91%

Kobavashi. S.: Nishio, K. J. Org. Chem., 1995, 60, 6620

Section 36

Alcohols from Amides

20% ZnBr2

PhCHO

23

H->O ——

*-

THF, 3h, 25°C

Ph-^"^ CgH 17

Zheng, B.; Srehnik. M. J. Org. Chem., 1995, 60, 3278 In, H20, 30 min

„

H

,Br

Li. C.-J. Tetrahedron Lett., 1995, 36, 517

Me LTi(OiPr)4,iPrMgCl

-CHO Ph

^ 3.H20

pH

x

ptf

(16 : 84) 81% Harada, K.; Urabe, H.; Sato. F. Tetrahedron Lett., 1995, 36, 3203 Nakagawa, T.; Kasatkin, A.; Sato. F. Tetrahedron Lett., 1995, 36, 3207 CHO ^^v_^°

l.TMSOTf,CH£l 2 , -78°C 2. Bu3SnCH2CH=CH2 -40°C 3. TBAF

(>99

:

<1) 98%

Kim. S.: Kim, S.H. Tetrahedron Lett., 1995, 36, 3723 H

,aq.NH4Cl PhCHO sonoelectro-produced Zn powder

Phx

82% Durant, A.; Delplancke, J.-L.; Winand, R.; Reisse, ]. Tetrahedron Lett., 1995, 36, 4257

99% THF,6h OH Sarangi, C.; Nayak, A.; Nanda, B.; Das. N.B.: Sharma, R.P. Tetrahedron Lett., 1995, 36, 7119

24

Compendium of Organic Synthetic Methods, Vol 9

Section 34B

Br CHO

^ ^

>^

^^ ^SiMe3

In, H2O, rt 62% (15:25 E:Z) Isaac, M.B.; Chan. T.-H. Tetrahedron Lett., 1995, 36, 8957

(74 : Miyoshi, N.; Kukuma, T.; Wada, M. Chem. Lett., 1995, 999 l.Ti(OiPr)2,2iPrMgBr

.Br

2. PhCHO OH Kasatkin, A.; Nakagawa, T.; Okamoto, S.; Sato. F. J. Am. Chem. Soc., 1995, 117, 3881 l.LDBB,THF,-78°C 2.MnCl 2 ,THF,-78°C

*" SPh

HO

•CHO

LDBB = 4,4'-di-r-butylbiphenylide

-78°c ~> °°c

g4% (44.56)

Ahn, Y.; Doubleday, W.W.; Cohen, T. Synth. Commun., 1995, 25, 33

O

"*

Q \

""""O

PhCHO, 10% PdCPhCN)^ 3 SnCl2»2 HP, DMI, 25°C

HQ,,

"

91% Rang. S.-K.: Park, D.-C.; Park, C.-H.; Jang, S.-B. Synth. Commun., 1995, 25, 1359

Section 36

Alcohols from Amides

25

, Sn , Me3SiCl -Bu4NBr,MeOH,rt,4h Zhou, J.-Y.; Yao, X.-B.; Chen, Z.-G.: Wu. S.-H. Svnth. Commun., 1995, 25, 3081 PhCHO

, THF, rt, 4d

PhCHO PtCl2(PPh3)2 90% phx^ \x^"^ Nakamura, H.; Asao, N.; Yamamoto. Y. J. Chem. Soc. Chem. Commun., 1995, 1273 _

OH

I

)H

CeHisCHO CH2C12-H2O (9.1 : 9) 48% H2O , BU4NBr (1 : 99) 48% Masuyama. Y.: Kishida, M.; Kurusu, Y. J. Chem, Soc. Chem, Commun., 1995, 1405 REVIEW: "Synthetic Organoindium Chemistry: What Makes Indium So Appealing," Cintas. P. Synlett, 1995, 1087 SECTION 35:

ALCOHOLS AND THIOLS FROM ALKYLS, METHYLENES AND ARYLS

No examples of the reaction RR1 -» ROH (R1 = alkyl, aryl, etc.) occur in the literature. For reactions of the type RH -» ROH (R = alkyl or aryl) see Section 41 (Alcohols and Phenols from Hydrides). NO ADDITIONAL EXAMPLES

SECTION 36: ALCOHOLS AND THIOLS FROM AMIDES O

LiBH3P-Pyr,THF,25°C N \

^w J

Pyr = pyrrolidino

Fisher, G.B.; Fuller, J.C.; Harrison, J.; Goralski, C.T.; Singaram. B. Tetrahedron Lett., 1993, 34, 1091

8

26

Compendium of Organic Synthetic Methods, Vol 9

Section 39

SECTION 37: ALCOHOLS AND THIOLS FROM AMINES NO ADDITIONAL EXAMPLES SECTION 38: ALCOHOLS AND THIOLS FROM ESTERS P(Cy)3 ,180°C, 15h HO—Bu 68% H^^( •OBu Vega, F.R.; Clement, J.-C.; des Abbayes, H. Tetrahedron Lett., 1993, 34, 8117

OMe

Mg, MeOH, rt, 2.5h

,OAc MeO"

^"

"^

MeO

Xu. Y.-C.: Lebeau, E.; Walker, C. Tetrahedron Lett., 1994, 35, 6207 1. PMHS , Ti(OiPr)4 , THF Ph—CO2Me

*-

PhCH2OH

2. NaOH

0/C(, 863>

PMHS = polymethylhydrosiloxane Breedon, S.W.: Lawrence. N.J. Svnlett. 1994, 833 1. 2.5 eq. PHMS , 25% Ti(OiPr)4 C9H19—C02Et

65°r id ML"*

PH

^

2. aq. NaOH, THF Reding, M.T.; Buchwald. S.L. J. Org. Chem., 1995, 60, 7884 C7Hi5CH2SAc

BER, Pd(OAc)2, MeOH, reflux

*- C7Hi5CH2SH

BER = borohydride exchange resin Choi, J.; Yoon. N.M. Svnth. Comtnun., 1995, 25, 2655 SECTION 39:

og«

ALCOHOLS AND THIOLS FROM ETHERS, EPOXIDES AND THIOETHERS Bu2CuCNLi2, THF

P"

QH r-BuMe2Si

products are converted to alkenes via

(95

Swern oxidation and elimination Chauret, D.C.; Chong. J.M. Tetrahedron Lett., 1993, 34, 3695

:

5) 80-90%

Section 39

Alcohols from Ethers

27

OH Al(Hg) , 10% aq. NaHCO3 linn HBlOH

95%EtOH,rt ultrasound

also used Zn rather than Al(Hg) yield is 23% ^^ ultrasound Mirando Moreno. M.J.S.: Sae Melo, M.L.; Campos Neves, A.S. Tetrahedron Lett., 1993, 34, 353 Salvador, J.A.R.; Sae Melo. M.L.: Campos Neves, A.S. Tetrahedron Lett., 1993, 34, 361

Phi, Pd(PPh3)^Cl2 , Zn , ZnCl2 THF, 60°C , 4h , NEt3 86%

Duan, J.-P.; Cheng. C.-H. Tetrahedron Lett., 1993, 34, 4019 1. Lil, MeCN , Amberlyst 15 rt, 30 min 2. BuaSnH, AIBN, 80°C QH 99x88% toluene, 2h Federici, C.; Righi. G.: Rossi, L.; Bonini. C.: Chiummiento, L.; Funicello, M. Tetrahedron Lett., 1994, 35, 797

^OTMS

HO

Me

Bach. T. Tetrahedron Lett., 1994, 35, 1855

'OH , 10%Pd(OAc)2 5 eq. NaO2CH, 2 eq. Bu^Cl 3 eq. iPr2NEt, 80°C, Id N,N-dimethylacetamide (69:31 E:Z) Larock. R.C.: Ding, S. J. Org. Chem., 1993, 58, 804

' 70%

28

Compendium of Organic Synthetic Methods, Vol 9

"

Section 39

HO '*N H

BnO

,

.C02Me

^

Pak. C.S.: Lee, E.; Lee, G.H. J. Org. Chem., 1993, 58, 1523 ~

Pd/C, HCO2NH4, EtOH

OH

23°C , 2d 81%

Dragovich. P.S.: Prins, T.J.; Zhou, R. J. Org. Chem., 1995, 60, 4922

10% Pd(PPh3)4 , NaBH4 —-- r-B 2. 1NHC1

Beugelmans, R.; Bourdet, S.; Bigot, A.; Zhu. J. Tetrahedron Lett., 1994, 35, 4349

O

Te , LiBHEt3 , rt 3h

TsO Kumar, A.; Dittmer. D.C. Tetrahedron Lett., 1994, 35, 5583

\

L-Selectride , THF , 67°C , 12h -OMe -

Maietich. G.: Zhang, \.; Wheless, K. Tetrahedron Lett., 1994, 35, 8727 O

1 • TMSN3 , W(Nf-Bu)2(NHI/-Bu)2 , 5d 2.H+

PhX"\x'OH

95%

[ with Cr(Nf-Bu)2Cl2; 12h — 95% ] Leung. W.-H.: Chow, E.K.F.; Wu, M.-C; Kum, P.W.Y.; Yeung. L.-L. Tetrahedron Lett., 1995, 36, 107

Section 40

Alcohols from Halides

29

9H

5% SmI/THF)2, CH2C12 Et2NH, rt, 18h

(100 : regioselectivity of addition reversed with Me3SiN3 to form azide-OTMS Van de Weghe, P.; Collin. J. Tetrahedron Lett., 1995, 36, 1649

0) 63%

,— ~ ' j O

i^

.OTMS

TMSN3 , PtLjSbOH , PhH

reflux, 2h / 67% 19% Fujiwara. M.: Tanaka, M.; Baba, A.; Ando, H.; Souma, Y. Tetrahedron Lett., 1995, 36, 4849

1. e", Ni(II), Mg anode, DMF, rt

,OPh

PhOH 2.H2O 99%

Olivero, S.; Dufiach. E. /. Chem. Soc. Chem. Commun., 1995, 2497 Additional examples of ether cleavages may be found in Section 45 A (Protection of Alcohols and Thiols).

SECTION 40:

ALCOHOLS AND THIOLS FROM HALIDES AND SULFONATES Na3SPO3, MeOH -Br

^

O2

reflux, overnight Bieniarz. C.: Cornwall, M.J. Tetrahedron Lett., 1993, 34, 939 Br

SiMe3

1. Li dispersion , ether reflux 2. PhCHO, -10°C ih iu

~**~

~ri'»^

SiMe3

also works with ketones Takahashi. M.: Hatano, K.; Kimura, M.; Watanabe, T.; Oriyama, T.; Koga, G. Tetrahedron Lett., 1994, 35, 579

30

Compendium of Organic Synthetic Methods, Vol 9

l.Me3ZnLi,THF,-78°C

Ph—I

2. Me3Al, CH£12 , 0°C , Ih

-

Section 42

T

PIT*"\

55% Kondo, Y.; Takazawa, N.; Yamazaki, C.; Sakamoto. T. J. Org. Chetn., 1994, 59, 4717

.

5

PhCHO

H

, r-BuLi, -78°C

*- PhCHCl2 2. NaBO?4 HP, 2h 64%

Kabalka. G.W.: Lin, N.-S.; Yu, S. Tetrahedron Lett., 1995, 36, 8545

NHBn

Ag 2 0,MeCN,Hp

12h O Yang, R.-Y.; Dai. L.-X. Synth. Commun., 1994, 24, 2229

l.HCOzNHEts C02H

*•

C02H

Alexander. J.: Renyer, M.L.; Veerapanane, H. Synth. Commun., 1995, 25, 3875 SECTION 41: ALCOHOLS AND THIOLS FROM HYDRIDES . e', CF3CO2H, CH2C12, NEt3

\_J

T^

\_J

73% Fujimoto, K.; Maekawa, H.; Tokuda, Y.; Matsubara, Y.; Mizuno, T.; Nishiguchi. I. Synlett. 1995,661

SECTION 42: ALCOHOLS AND THIOLS FROM KETONES The following reaction types are included in this section: A. Reductions of Ketones to Alcohols B. Alkylations of Ketones, forming Alcohols Coupling of ketones to give diols is found in Section 323 (Alcohol —» Alcohol).

Section 42A

Reduction of Ketones

31

SECTION 42A: REDUCTION OF KETONES TO ALCOHOLS ASYMMETRIC REDUCTION

A

BH 3 , THF, 80°C ___; ph

QH |

^

-VQ_ ..

> 90%

™X\

(92% ee, R)

H Quallich. G.J.: WoodaU, T.M. Tetrahedron Lett., 1993, 34, 4145 « Ph/,,,,5' . 10% ^^—^i»Me>, BH3«SMe-2 -SMe-2 Me

. *"

PIT ^Me 2.1NHC1 Bolm. C.: Elder, M. Tetrahedron Lett., 1993, 34, 6041

OH |

G. candidium ,C02Et ^ cyclopentanol H 2 0,70h

I

O TT

?

J^ PlT ^Me

(76%ee,R)

hexane, 3h cyclopentanol

(l.y syn.an i) G.candidium = Geotrichum candidum Nakamura. K.i Takano, S.; Ohno, A. Tetrahedron Lett., 1993, 34, 6087 0.6 BH3»SMe2, THF rt,
Me

10%

1

« Jj

r

"

Me

f

"

82% (27%ee,S)

Bums, B.; Studley, J.R.; Wills. M. Tetrahedron Lett., 1993, 34, 7105

Me3SiCl 2.2NHC1

Me '" 92% (84% ee, R) Bolm. C.: Seger, A.; Felder, M. Tetrahedron Lett., 1993, 34, 8079

Me

Me

32

Compendium of Organic Synthetic Methods, Vol 9

Section 42A

H

N OH

^ ,BuLi,THF OH

2.SmI 3 ,THF,ICH£H 2 I 3. quench quant. (97% ee , R) Evans. D.A.: Nelson, S.G.; Gagn6, M.R.; Muci, A.R. J. Am. Chem. Soc., 1993, 115, 9800 1 . P-TADDOL complex , Ph2SiH2 , PhH

OH

50% (29.5:70.5 R:S)

[Rh(cod)Cl]2 2. TsOH, MeOH

TADDOL = a,a,a',a'-tetraaryl-4,5-dimethoxy-l,3-dioxolane Jakaki, J.-i.; Schweizer, W.B.: Seebach. D. Helv. Chim. Acta, 1993, 76, 2654

I

OAcC

Bakers yeast (cell free extract) *~ NaDPH, 8h

OH

62% (>99% ee, S) Ishihara, K.; Sakai, T.; Tsuboi, S.; Utaka. M. Tetrahedron Lett., 1994, 35, 4569

[ (COD)Rh(DiPFc) ]+ OTf

O -"\

P I T ^ OH

60 psi H 2 , 25°C, 4h

DiPFc = l,l'-bis-(diisopropylphosphino)ferrocene quant. Burk. M.J.: Harper, T.G.P.; Lee, J.R.; Kalberg, C. Tetrahedron Lett., 1994, 35, 4963

H

>95%(91.7%ee,S) Cl

BH3»THF, THF, rt 3 . .

^^

Cl

Hong, Y.; Gao. Y.: Nie, X.; Zepp, C.M. Tetrahedron Lett., 1994, 35, 6631 1. Ph2SiH2 ,5% Rh-diferrocenyl67% (50% ee, R) 6 2.0.5M HCl/MeOH OH Nishibayashi, Y.; Singh, J.D.; Segawa, K.; Kukuzawa, S.i.; Uemura. S. /. Chem. Soc. Chem. Commun., 1994, 1375

Section 42A

Reduction of Ketones

Bakers yeast ' sugar

33

r-u oli | +

,CO2Et

A.

(77 : 55% ee Nielsen, J.K.; Madsen. J.0. Tetrahedron Asymmetry, 1994, 5, 403

23)

immobilized Geotrichum candidum Me

Ph

hexane 2-hexanol

.,CO2Et

QH Me

Ph

73% (>99% ee, S) Nakatnura. K.: Inoue, Y.; Ohno, A. Tetrahedron Lett., 1995, 36, 265

OH

OH

(-)-B -chlorodiisopinocampheylborane -15°C -> 0°C, THF, pyridine

99% (96.4% ee) Shieh. W.-C.: Cantrell Jr., W.R.; Carlson, J.A. Tetrahedron Lett., 1995, 36, 3797 H 2 , (S-BINAP)2RuBr2 C02Me

9H

Me OH,rt,48h

Genet. J.P.: Ratovelomanana-Vidal, V.; Cano de Andrade, M.C.; Pfister, X.; Guerreiro, P.; Lenoir, J.Y. Tetrahedron Lett., 1995, 36, 4801

JL

H2 , iPrOH , chiral bis-phosphine

>99% (87% ee, R) Ph—~ "* chiral bis-amine Ph* Ohkuma, T.; Ooka, H.; Hashiguchi, S.; Ikariya, T.; Novori. R. J. Am. Chem. Soc., 1995, 117, 2675 [RuCl2(mesitylene)]2, KOH , 15h TolO2SHN,

OH

NH2

95% (97% ee, S) Hashiguchi, S.; Fujii, A.; Takehara, J.; Ikariya, T.; Novori. R. 7. Am. Chem. Soc., 1995, 117, 7562

34

Compendium of Organic Synthetic Methods, Vol 9

1. Ph2SiH2,THF, 1% RhCl(NBD)2L chiral ferrocenylphosphineligand ^

Section 42A

QH

Y

90%(87%ee,S)

2.H30+ Plr^\ Havashi. T.: Hayashi, C.; Uozumi, Y. Tetrahedron Asymmetry, 1995, 6, 2503 || i.-*^ PIT

1.0.1 chiral diol, hexane, -3°C, catecholborane + o H tr r»+ 2. 30

Ph'

quant. (82% ee) Giffels, G.; Dreisbach, C.; Kragl, U.; Weigerding, M.; Waldmann, H.; Wandrey. C. Angew. Chem. Int. Ed. Engi, 1995, 34, 2005 )H

NaBH4,EtOH Co (p-oxoaldiminato) complex

99% (73% ee, S) Nagata, T.; Yorozu, K.; Yamada, T.; Mukaivama. T. Ansew. Chem. Int. Ed. Engl., 1995, 34, 2145

NON-ASYMMETRIC REDUCTION 1. CdCl2/Mg (powder) THF, 15 min — ^ 2 H2 \ / ° Bordoloi. M. Tetrahedron Lett., 1993, 34, 1681

O

LiAlH(OCEt2CMe3)3

/ ( \

\ )—OH 92% /

^ t-Eu

(

OH

)

THF

with LiAlH(OCMe3)3 - 90:10 trans:cis Boireau. G.: Deberly, A.; Toneva, R. Synlett, 1993, 585

5.95 trans:cis

Cu(II) exchanged cationic resin f-Bu

(

>=O

»-

r-Bu

NaBH 4 ,EtOH,0°C Sarkar. A.: Rao, B.R.; Ram, B. Synth. Commun., 1993, 23, 291

(

)

OH

Section 42A

Reduction of Ketones

35

)H

THF, 25°C , 3h

C

92%

N-BH3 Li

Fuller, J.C.; Staangeland, E.L.; Goralski, C.T.; Singaram. B. Tetrahedron Lett., 1993, 34, 257 / < \

\ >==0 /

iPrOH, SiO2-Zr catalyst

^

rettux

/ ( \

\ V-OH / *

Inada. K.: Shibagaki, M.; Nakanishi, Y.; Matsushita, H. Chem. Lett., 1993, 1795 )Me

TiCl4, Me4NBH4 CH2C12, -78°C other reducing agents also used

^^

.

1) 93%

Sarko, C.R.; Guch, I.C.: DiMare. M. J. Org. Chem., 1994, 59, 705 LiBH3N(n-C3H7)2 THF,0°C

r-Bu *— ^"-/r 99% Harrison, J.; Fuller, J.C.; Goralski, C.T.; Singaram. B. Tetrahedron Lett., 1994, 35, 5201 OH

1. Cp2TiCl2/NaBH4, 5 min 2. INNaOH

90%' Barden, M.C.; Schwartz. J. J. Org. Chem., 1995, 60, 5963

(MeO)3SiH , LiOMe, ether


(8 92) quant. : wth (MeO)3SiH/HMPA/LiOMe/0°C/2h -» (90:10) 98% Hojo, M.; Fujii, A.; Murakami, C.; Aihara, H.; Hosomi. A. Tetrahedron Lett., 1995, 36, 571

36

Compendium of Organic Synthetic Methods, Vol 9

Section 42B

H2 (8 aim), cat. RuCl2(Binap)(dmf)n - H<

iPrOH, diamine, KOH , 28°C

Ph Ph Ohkuma, T.; Ooka, H.; Ikariya, T.: Novori. R. J. Am. Chem. Soc., 1995, 117, 10417

O

cat. [NiCl2(PPha)2, cat. NaOH

QH 82%

iPrOH , AT , 30h , heat P Iver. S.: Varghese, J.P. / Chem. Soc. Chem. Commun., 1995, 465

SECTION 42B: ALKYLATION OF KETONES, FORMING ALCOHOLS Aldol reactions are listed in Section 330 (Ketone- Alcohol)

e' , SmCl3 , DMF , 20°C Hebri, H.; Dufiach. E.: P6richon, J. Tetrahedron Lett., 1993, 34, 1475

a

3 eq. Me2S=CH2 , THF -10°C ->

rt

( I

\ >°H ^J^^

91% Harnett, J.J.; Alcaraz, L.; Mioskowski, C.; Martel, J.P.; LeGall, T.; Shin, D.-S.; Falck. J.R. Tetrahedron Lett., 1994, 35, 2009

CH3

DMF.____,

QH

89% Shono. T.: Morishima, Y.; Moriyoshi, N.; Ishifune, M. J. Org. Chem., 1994, 59, 273

Section 42B

Alkylation of Ketones

37

-OH

1.2.2 eq. SmI2 , THF 2 eq. f-BuOH 2. H3O+

53% (1:1) Molander. G.A.: McKie, J.A. / Org. Chem., 1994, 59, 3186

0.05 CeCl3, Ih, THF

•- '\ O

' lOH ^^.

1.1 =x MgBr

93% Dimitrov. V.: Bratavanov, S.; Simova, S.; Kostova, K. Tetrahedron Lett., 1994, 35, 6713

OH

76%

Li. C.-J.: Lu, Y.-Q. Tetrahedron Lett., 1995, 36, 2721

,OH THF,1.5h uses commercial Zn dust Ranu. B.C.: Majee, A.; Das, A.R. Tetrahedron Lett., 1995, 36, 4885 OH

1.8 Et2Zn , Ti(OiPr)4, hexane PhCHO

80%

^

-23°C , 0.1 chiral catalyst Zhang. X.: Guo, C. Tetrahedron Lett., 1995, 36, 4947 Me3Ti«MeLi, ether

JL

97% 99%ee,S

II

H

Q

-50°C selective for conjugated ketones in the presence of non-conjugated ketones Marko. I.E.: Leung, C.W. J. Am. Chem. Soc., JPP4, 116, 371

Me

38

Compendium of Organic Synthetic Methods, Vol 9

Section 42B

OH

1.10% Cp2Ti(PMe3)2, Ph2SiH2 toluene 2. HCl/acetone, -20°C

I

V""•

>60% Kablaoui, N.M.; Buchwald. S.L. 7. Am. Chem. Soc., 1995, 117, 6785

e", MeCN, ZnBr2 Bu4N BF4

-/-Vx

u

+

(95 : 5) 85% Rollin. Y.: Derien, S.; Dufiach, E.; Gebehenne, C.; Perichon, J. Tetrahedron, 1993, 49, 7723

.Br

O

:o2Et

Zn, aq. NH4C1, THF

HO

C02Et (54

Ahonen, M.; Sjoholm. R. Chem. Lett., 1995, 341 -I

THF,-60°C

77%

Wipf. P.: Lim, S. J. Chem. Soc. Chem. Commun., 1993, 1655 l.CeCl 3 ,THF,0°C OH

3.10% AcOH 70% Bartoli. G.: Marcantoni, E.; Petrini, M. Angew. Chem. Int. Ed. Engl, 1993, 32, 1061

Section 44

Alcohols from Alkenes

39

SECTION 43: ALCOHOLS AND THIOLS FROM NITRILES 1. Li (excess), PhCHO, -30°C

MeCN

5% 4,4-bis-t-Bu biphenyl

^

?H II Me*^"^ ph

39%

2. H 2 O, HC1 Guijarro, D.; Yus. M. Tetrahedron, 1994, 50, 3441

SECTION 44: ALCOHOLS AND THIOLS FROM ALKENES

cH2ci2 2 c

. l.Ti(BH 4 ) 3 ,30min

..

r T

- °° .

2.10%K2C03

k^

(1 1.2) 82% : Kumar, K.S.R.; Baskaran, S.; Chandrasekaran, S. Tetrahedron Lett., 1993, 34, 171 Me

Zn(BH4)2, DMF

,/\>^

SiO 2 ,rt,30min

- \XX» I """OH J

+

(70 : Ranu. B.C.: Charkraborty, R.; Saha, M. Tetrahedron Lett., 1993, 34, 4659

30) 80%

l.Mg*,THF,rt 2. ethylene oxide THF, -78°C 3. CO2, 0-C -»rt 4. H 3 O + , 0°C 69%

fiAQJ, 50

u/ifh

'° W1U1 H30+at-78°C Sell, M.S.; Xiong, H.; Rieke. R.D. Tetrahedron Lett., 1993, 34, 6007, 6011 Mg* = 8 Li, naphthalene, 4 MgCl2, THF, 3 Li

1.2eq.PhO 2 BH,THF Nb catalyst, 25°C , Id 71%

2. H2O2, NaOH

^ ,

Burgess. K.: Jaspars, M. Tetrahedron Lett., 1993, 34, 6813 also with Cp2TiCl4, see Burgess. K.: van der Donk, W.A. Tetrahedron Lett., 1993, 34, 6817

"'OH

40

Compendium of Organic Synthetic Methods, Vol 9

Section 44

l.PhaSiSH.AIBN 2.TFA

74%

Hach6, B.; Gareau. Y. Tetrahedron Lett., 1994, 35, 1837 buffered AD-mix-p , 0°C

OH

f-BuOH-H2O, MeSO2NH2 (70%ee) Vanhessche, K.P.M.; Wang, Z.-M.; Sharpless. K.B. Tetrahedron Lett., 1994, 35, 3473 1. catecholborane, 10% SmI3,18h 79% 2. oxidation C8H17. ^\ *^^ OH (50:1 l°::

C8H17 \

Evans. D.A.: Muci, A.R.; Stunner, R. /. Org. Chem., 1993, 58, 5307

,-25°C

1

_

OH

74% (76% ee S)

new asymmetric borane ^f Dhokte, U.P.; Brown. H.C. Tetrahedron Lett., 1994, 35, 4715

'

OH

. Et2BH 2. Et2Zn

^

pt

3. PhCHO, Ti(OiPr)4 NHTf

a

'NHTf Schwink, L.; Knochel. P. Tetrahedron Lett., 1994, 35, 9007 OH 1

1.4 EtMgCl , ether , 25°C , 12m 5% CP2ZrCl2

^

^^

2.0 2 ,0°C

67% (80% ee)

OH I .A. ^~\ - C9H1
Houri, A.F.; Didiuk, M.T.; Xu, Z.; Koran, N.R.; Hovevda. A.H. J. Am. Chem. Soc., 1993, 115, 6614

Section 45

Alcohols from Misc.

41

SiO2,Zn(BH4)2 ,DME,rt

95% Ranu. B.C.: Sarkar, A.; Saha, M.; Chakraborty, R. Tetrahedron, 1994, 50, 6579

1 . Co(tdcpp) , O2 , Et3SiH JPrQH , CH2C12_

J Ph

OH

^

2. P(OMe)3

tdcpp = 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphinato Matsushita. Y.: Sugamoto, K.; Matsui, T. Chem. Lett., 1993, 925 1. HSiCl3 , MeOVMOP , 40°C , Id 2. H2O2 , KF , KHCO3 83x71% (93% ee) Uozumi, Y.; Kitayama, K.; Hayashi. T.: Yanagi, K.; Fukuyo, E. Bull. Chem. Soc. Jpn., 1995, 68, 713

SECTION 45:

ALCOHOLS AND THIOLS FROM MISCELLANEOUS COMPOUNDS H

. MOM-C1, iPr2NEt, CH2C12

Mevers. A.I.: Shimano, M. Tetrahedron Lett., 1993, 34, 4893 rr5

OMe

OMe

hv , CO, THF

x^^sX'^^/'

^^^\ Merlic. C.A.: Roberts, W.M. Tetrahedron Lett., 1993, 34, 7379

65%

42

Compendium of Organic Synthetic Methods, Vol 9

Section 45A

1. TBAF , THF , rt Ci2H25—SiMe2SiMe3 2. H2O2 , KHCOa MeOH , 40°C

65%

Suginome, M; Matusnaga, S.; Ito. Y. Synlett. 1995, 941 SECTION 45A: PROTECTION OF ALCOHOLS AND THIOLS PdOH^.MeOH _ ^\ ^ — ^ HCT (CH2)5 cyclohexane , 30 mm Cormier. J.F.: Issac, M.B.; Chen, L-F. Tetrahedron Lett., 1993, 34, 243 ^\ ^ Me2r-BuSiCT (CH2)5

OH

3

OH

90%

Py, CH2C12 87%

C13CO 'OCC13 Burk. R.M.: Roof, M.B. Tetrahedron Lett., 1993, 34, 395 H

10%FSO3H,rt, 30min xs

~ ^

-*"

OSiMe3

,SiMe3

Lipsmitz. B.H.: Burgess-Henry, J.; Roth, G.P. Tetrahedron Lett., 1993, 34, 995 J + 'OSO2-O-OSO20

p

0.67 h , 95%

Jung, J.C.; Choi, H.C.; Kim. Y.H. Tetrahedron Lett., 1993, 34, 3581

>C )

OH

r-BuPh2SiCl, DMF ld

' ' 87% CAUTION: NH^O, & NH4C1O4 o nOH/15 min - 83%] [w/ AgN fc 3/B are potentially explosive Hardinger. S.A.: Wijaya, N. Tetrahedron Lett., 1993, 34, 3821

Section 45 A

Protection of Alcohols

43

dihydropyran, CH2C12, rt , Bu^

^ OH

Bu

r [Rh(MeCN)3(triphos)] [OTfJ2

>^ ^OTHP ^X^

Ma, S.; Venanzi. L.M. Tetrahedron Lett., 1993, 34, 5269

, BF3OEt2

i

—^-

yo-/c

V,^^

ROTAM group see Tetrahedron Lett., 1988, 29,2951 Figadere. B.: Franck, X.; Cav6, A. Tetrahedron Lett., 1993, 34, 5893 F3-2 AcOH , rt , 20 sec

OH

I

2. H202 , KF , NaHC03 MeOH , THF , rt , 3d

y:o2Me

Vv^ ™

77%

Reming. I.: Winter, S.B.D. Tetrahedron Lett., 1993, 34, 7287 l."Cp2Zr"

OH

97% 2.H30+ = Cp2ZrCl2/BuLi - see Tetrahedron Lett., 1986, 27, 2829 Ito, H.; Taguchi. T.: Hanzawa, Y. J. Org. Chem., 1993, 58, 774 PhCH2OH

MoO2(acac)2 , CH2(OMe)2 , reflux -^

PhCH2OCH2OMe

85%

Kantam. M.L.: Santhi, P.L. Synlett, 1993, 429 .OTBDPS (CH2)10

7

BCl3-SMe2 , ether , Id

HO^

^

OTBDPS

(CH2)io

93% Congreve, M.S.; Davison, E.G.; Fuhry, M.A.M.; Holmes. A.B.: Payne, A.N.; Robinson, R.A.; Ward, S.E. Synlett, 1993, 663

44

Compendium of Organic Synthetic Methods, Vol 9

A12O3 microwave, 9 min

Section 45A

/ (

CMe3

\ ) OH /

Lev. S.V.: Mynett, D.M. Synlett, 1993, 793 1. Bu2Sn(OMe)2, PhH, reflux Dean-Stark

|H

QH Bn

2. PhCH2Br

'

Boons, G.-J.; Castle, G.H.; Clase, J.A.; Grice, P.; Lev. S.V.: Pinel, C. Synlett, 1993, 913 dihydropyran, hexane HY zeolite, reflux, 1.5h

Bu

Kumar. P.: Dinesh, C.U.; Reddy, R.R.; Pandev. B. Synthesis, 1993, 1069 dihydropyran, CAN, MeCN it, 30 min

Maity, G.; Rov. S.C. Synth. Commun., 1993, 23, 1667

OH MoO2(acac)2, reflux, 4h Kantam. M.L.: Santhi, P.L. Synth. Commun., 1993, 23, 2225

AcO

k

/) ff

(CH2)3OAc

alumina, 30 sec

68%

OTHP

H

microwave

with 2.5 min of microwave, obtain 92% bis deacetylation 93% Varma. R.S.: Vanna, M.; Chatterjee, A.K. J. Chem. Soc., Perkin Trans. 1., 1993, 999 MOM-C1, Na-X-zeolite

CHz2C1z2, reflux

Bu,

90%

Kumar. P.: Raju, S.V.N.; Reddy, R.S.; Pandey, B. Tetrahedron Lett., 1994, 35, 1289

Section 45 A

Protection of Alcohols

OTHP

45

1 • 5% EtSH , 10% BF3OEt2 CH2C12 , -20°C -» 0°C 2. aq. NaHCO3

>SiMe2r-Bu

^k

JDSiMe^-Bu

cleavage of THP ethers in the presence of other acid labile functional groups Nambiar. K.P.: Mitra, A. Tetrahedron Lett., 1994, 35, 3033

/

Q , Al2O3,ZnCl2

rt, 15 min

Ranu. B.C.: Saha, M. J. Org. Chem., 1994, 59, 8269 DTBDMS

PTBDMS

pH

^ EtOH, 50°C, Ih

94% Prakash. C.: Saleh, S.; Blair, I.A. Tetrahedron Lett., 1994, 35, 7565

85%

TMSHN HOOC(CH2)i50H cat. TBAF , CH£12 , 0°C quant other silazanes can be used as well Tanabe. Y.: Murakami, M.; Kitaichi, K.; Yoshida, Y. Tetrahedron Lett., 1994, 35, 8409 OH

HIP-OH , DEAD , PPh3

LiNaphth , THF, -78°C HIP-OH = (CF3)2CPhOH Cho, H.-S.; Yu, J.; Falck. J.R. .7. Am. Chem. Soc., 1994, 116, 8354

46

Compendium of Organic Synthetic Methods, Vol 9

X

Dowex 50W-X8 ,25h C02Me

,O

Section 45A

90%MeOH

OBz

OH

OH

OBz

87%

Park, K.H.; Yoon, Y.J.; Lee. S.G. Tetrahedron Lett., 1994, 35, 9737

OSiMe3 90%

A12O3 , 3% H20, 5 min Feixas, J.; Capdevila, A.; Guerrero. A. Tetrahedron, 1994, 50, 8539 OTHP

/

OTHP

NaCNBH3, BF3-OEt2 rt,2h

Srikrishna. A.: Sattigeri, J.A.; Viswajanani, R.; Yelamaggad, C.V. /. Org. Chem., 1995, 60, 2260 1. AcCl, ZnCl2, ether

OAc

OCH2OMe

2. MeOH, ether, iPr2NEt

X^X

97%

Bailev. W.F.: Zarcone, L.M.J.; Rivera, A.D. J. Org. Chem., 1995, 60, 2532 10% TfOSiMe2f-Bu , CH2C12

-.

82%

Franck, X.; Figadere. B.: Cav6, A. Tetrahedron Lett., 1995, 36, 711

Section 45 A

BnO

Protection of Alcohols

^^

^ti

^1

47

!%I 2 ,MeOH

OH

•OMe Vaino, A.R.; Szarek. W.A. Svnlett. 1995, 1157 =\

OAc Sm, I 2 , THF-MeOH

Yanada. R.: Negoro, N.; Bessho, K.; Yanada, K. Synlett, 1995, 1261 PhCH2OH

2 eq. dihydropyran , DMF, 60°C, 7h 1—— ! *-

PhCH2OTHP

88%

Miura, T.; Masaki. Y. Svnth. Commun., 1995, 25, 1981 dihydropyran , 5°C , 10 min OTHP

Envirocat EPZG

88% Bandgar. B.P.: Jagtap, S.R.; Aghade, B.B.; Wadgaonkar, P.P. Synth. Commun., 1995, 25, 2211 / ^

V ^

DDQ, MeCN, H20, 5h OTHP

^

/ /

V \

OH

90% Raina, S.; Singh. V.K. Synth. Commun., 1995, 25, 2395

REVIEW: "Silyl Ethers as Protective Groups for Alcohols. Oxidative Deprotection and Stability Under Alcohol Oxidation Conditions," Muzart. J. Synthesis. 1993, 11

48

Compendium of Organic Synthetic Methods, Vol 9

Section 48

CHAPTER 4 PREPARATION OF ALDEHYDES

SECTION 46: ALDEHYDES FROM ALKYNES NO ADDITIONAL EXAMPLES SECTION 47: ALDEHYDES FROM ACID DERIVATIVES f|

AlH(Of-Bu)3, diglyme-THF

Ph^\Q -78°C Cha, J.S.; Brown. H.C. J. Org. Chem., 1993, 58, 4732

j? Ph— \

1. PBu3 2. Zn-Cu, MeSO3H PIT ^^ ^Cl

3.10K2C03 quant.

Maeda, H.; Maki, T.; Ohmori. H. Tetrahedron Lett., 1995, 36, 2247

JL

C5Hi f^ ^ Cl

1. 2 eq. piperidine, THF, it 2.2 eq. NaEt2AIH2, rt, Ih

C5Hi f

H

74% Yoon. N.M.: Choi, K.I.; Gyoung, Y.S.; Jun, W.S. Synth. Commun., 1993, 23, 1775

SECTION 48: ALDEHYDES FROM ALCOHOLS AND THIOLS MnO2, Bentonite microwave 60% *OMe Martinez, L.A.; Garcfa, O.; Delgado, F.; Alvarez. C.: Patifio, R. Tetrahedron Lett., 1993, 34, 5293

Section 49

Aldehydes from Alkynes

TCM (trichloromelamine) CH2Cl2,rt,20h

PhCH2OH

49

*~

PhCHO

also oxidizes 2° alcohols to ketones Kondo. S.: Ohira, M.; Kawasoe, S.; Kunisada, H.; Yuki, Y. 7. Org. Chem., 1993, 58, 5003 5% CpRu(PPh3)6Cl, 10% (C2H5)3NHPF6 °H

*

ii

Trost. B.M.: Kulawiec, R.J. 7. Am. Chem. Soc., 1993, 115, 2027 hydrous zirconium (IV) oxide Me3SiCl , PhCHO , xylene 67% Kuno. H.: Shibagaki, M.; Yakahashi, K.; Matsushita, H. Bull. Chem. Soc. Jpn., 1993, 66, 1699

DMSO,rt also for the preparation of ketones and 1,2-diketones Frigerio. M.: Santagostino, M. Tetrahedron Lett., 1994, 35, 8019 Montmorillonite K-10 , pentane -K2Fe04,3h Delaude, L.; Laszlo. P.: Lehance, P. Tetrahedron Lett., 1995, 36, 8505 _

QJJ

PhCH2OH _ PDC/Adogen464_ Mohand, S.A.; Muzart. J. Svnth. Commun., 1995, 25, 2373

^

PhCHO 63%

phCHQ

SECTION 49: ALDEHYDES FROM ALKYNES Conjugate reductions and Michael Alkylations of conjugated aldehydes are Usted in Section 74 (Alkyls from Alkenes).

50

Compendium of Organic Synthetic Methods, Vol 9

Section 51

HO 70% DMF ^O ^ CHO Phillips, O.A.; Eby, P.; Maiti. S.N. Synth. Commun., 1995, 25, 87 1. Me3SiI, KOH , PhCHO

*PhCH2CHO 2. Si02 Lemini, C.; Ordofiez, M.; Perez-Flores, J.: Cruz-Almanza. R. Synth. Commun., 1995, 25, 2695

(

'CHO

•
^4-CHLi

° '2

^

2.H20 3. NaBO3 Schummer. P.: Hofle, G. Tetrahedron, 1995, 51, 11219 Related Methods:

^^

^CHO

85%

Aldehydes from Ketones (Section 57) Ketones from Ketones (Section 177) Also via: Alkenyl aldehydes (Section 341)

SECTION 50: ALDEHYDES FROM ALKYLS, METHYLENES AND ARYLS 1. (MeO)2CHNMe2 DMF, 140°C

,) //

CH3

OzN

(\

/)

CHO

2. 3 eq. NaIO4, THF

Vetelino, M.G.; Coe. J.W. Tetrahedron Lett., 1994, 35, 219

70% Ganin, E.; Amer. I. Svnth. Commun., 1995, 25, 3149

SECTION 51: ALDEHYDES FROM AMIDES NO ADDITIONAL EXAMPLES

Section 53

Aldehydes from Esters

51

SECTION 52: ALDEHYDES FROM AMINES

l.BuLi 2. H3O+

I!

^J

98 x 70%

Flippin. L.A.: Carter, D.S.; Dubree, H.J.P. Tetrahedron Lett., 1993, 34, 3255 Related Methods:

Ketones from Amines (Section 172)

SECTION 53: ALDEHYDES FROM ESTERS BU3 n H , PhH U 3SnH

C6H13

== ^ ^ /==/\^H / = \ x SPh \^H S Phs ]| 0.4% Pd(PPh3)4 j| 1::99 (E:Z) O O Kuniyasu, H.; Ogawa, A.; Sonoda. N. Tetrahedron Lett., 1993, 34, 2491

CO2Me

1. 5% Cp2TiCiyBuLi

polymethyl-hydrosiloxane THF 2. workup Barr, K.J.; Berk, S.C.: Buchwald. S.L. J. Org. Chem., 1994, 59, 4323 NaAlH(NEt2)3 , THF, 6h

65%

CHO

65% Cha. J.S.: Kim, J.M.; Jeoung, M.K.; Kwon, O.O.; Kim, E.J. Org. Prep. Proceed. Int., 1995, 27,95

Ca(BH4)2,1,5-cod, THF CnH23C02Me ^ CnH23CH2OH Narasimhan, S.; Prasad, K.G.; Madhavan, S. Synth. Commun., 1995, 25, 1689

95%

1. PhMe2SiLi, THF, -110°C MeCO2Me

^ MeCHO 2. CrO3 , DMSO, rt Heming. I.: Ghosh, U. /. Chem. Soc., Perkin Trans. 1., 1994, 257

70x74%

52

Compendium of Organic Synthetic Methods, Vol 9

Section 55

REVIEW: "Asymmetric Reductions of C-N Double Bonds. A Review," Zhu, Q.-C.; Hutchins. R.O. Org. Prep. Proceed. Int., 1994, 26, 193

SECTION 54:

ALDEHYDES FROM ETHERS, EPOXIDES AND THIOETHERS LiCL04. ether

O

-CHO

rt 6h

'

o

60%

Palani, N.; Balasubramanian. K.K. Tetrahedron Lett., 1995, 36, 9527 ,B" O

/

\

Bu

\

/

•o + V_A >—/ < O

/ N

V /

BU CHO

MABR, CH2C12, -20°C (0 : 100) 73% SbF3, PhH, 25°C (85 : 15) 62% Maruoka, K.; Murase, N.; Bureau, R.; Ooi, T.; Yamamoto. H. Tetrahedron, 1994, 50, 3663 LiTMP ,THF, 20°C

Yanagisawa, A.; Yasue, K.; Yamamoto. H./. Chem. Soc. Chem. Commun., 1994, 2103 Related Methods:

SECTION 55:

Ketones from Ethers and Epoxides (Section 174)

ALDEHYDES FROM HALIDES AND SULFONATES 1. iPrsSi-SH/KH 2. TB AF, THF

Ph

'

H pt

3 H220

88x73% Miranda, E.I.; Diaz, M.J.; Rosado, I.; Soderquist. J.A. Tetrahedron Lett., 1994, 35, 3221 Rane, A.M.; Miranda, E.I.; Soderquist. J.A. Tetrahedron Lett., 1994, 35, 3225 CgH17—Br

30 atm CO , SiH(SiMe3)3, PhH

^

CgH17—CHO + octane (16%) AIBN, reflux gQ% Ryu. I.: Hasegawa, M.; Kurihara, A.; Ogawa, A.; Tsunoi, S.; Sonoda. N. Synlett, 1993, 143

Section 58

Aldehydes from Nitrites

Br

53

1. PhLi, THF, -78°C 2.

{

N-CHO

Ie Me Hardcastle, I.R.; Quavle. P.: Ward, E.L.M. Tetrahedron Lett., 1994, 35, 1747 OMs

t;

MeMgBr, THF

Ranaivosata, J.-L.; Bellosta, V.; Wietzke, R. Synth. Commun., 1995, 25, 3109 CHBr2

CHO NaOAc, CaCO3 , 7h TBAB , H 2 O, reflux

THBr2 Mataka. S.: Liu, G.-B.; Sawada, T.; Tori-i, A.; Tashiro, M. J. Chem. Res. (S), 1995, 410 SECTION 56: ALDEHYDES FROM HYDRIDES NO ADDITIONAL EXAMPLES SECTION 57: ALDEHYDES FROM KETONES f HO

1. TMSC(Li)N2 , THF, iPr2NH -78°C -» reflux 2. H20

Ph

72%

Miwa, K.; Aovama. T.: Shioiri. T. S\nlett. 1994, 109 SECTION 58: ALDEHYDES FROM NITRILES PhCN

NaAlH(NEt2)3.THF,25°C ,

Cha. J.S.: Jeoung, M.K.; Kim, J.M.; Kwon, O.O.; Lee, J.C. Org. Prep. Proceed. Int., 1994, 26, 583

54

Compendium of Organic Synthetic Methods, Vol 9

Section 59

SECTION 59: ALDEHYDES FROM ALKENES Rh(acac)(CO)2,H2/CO 100atm,60°C,PhH,42h

Ph _.

P

+ Ph

CHO (90

: 10) > 99% conversion Higashizima, T.; Sakai, N.; Nozaki, K.; Takava. H. Tetrahedron Lett., 1994, 35, 2023

4 eq. PhSH , Et^NOTs , MeCN Ph S A P h S C H O V== e (0.05 Fmor1) Yoshida. J.: Nakatani, S.; Isoe, S. J. Org. Chem., 1993, 58, 4855

MPMOL

^L

^^

10% PdCl2/CuCl aq.DMF,O 2 ___ ^

77%

MPM

60°C, Id

Kang. S.-K.: Jung, K.-Y.; Chung, J.-U.; Namkoong, E.-Y.; Kim, T.-H. J. Org. Chem., 1995, 60, 4678

OHC

carbohydrate-OPAr2 catalyst

53% conversion 51%ee (96 : RajanBabu, T.V.; Avers. T.A. Tetrahedron Lett., 1994, 35, 4295

// h -"

.CHO

CO , H2

[Rh(cod)IOAc)]2

4)

Ph

(96 : Dovle. M.P.: Shanklin, M.S.; Zlokazov, M.V. Synlett, 1994, 615

4) 94%

Section 60A

Protection of Aldehydes

r\

55

Rh(acac)(CO)rBINAPHOS

N H2/CO (100 atm) , PhH, 60°C , 62h / CHQ Sakai, N.; Nozaki, K.; Takava. H. J. Chem. Soc. Chem. Commun., 1994, 395

CO, H 2 ,5% Rh(cod)L BF4 PhH , 55°C

I Ph

CHO

CHO

L = bisphosphine (35 . j) Chan. A.S.C.: Pai, C.-C.; Yang. T.-K.: Chen, S.-M. J. Chem. Soc. Chem. Commun., 1995, 2031 Related Methods: SECTION 60:

Ketones from Alkenes (Section 179)

ALDEHYDES FROM MISCELLANEOUS COMPOUNDS

N-OH

O

MeCN, CuCl2-2 H2O

H

H

Singh, L.; Ram. R.N. Svnth. Commun., 1993, 23, 3139 Ph

=N

H I

TMSCl,NaNO2,CCl4

/N\^x

*•

Y

PhCHO

95%

Aliquat 336 O Khan. R.H.: Mathur, R.K.; Ghosh, A.C. J. Chem. Res. (S), 1995, 506

SECTION 60A: PROTECTION OF ALDEHYDES OAc r Al2Os (neutral), microwave Ph ( *• Ph—CHO \ CH2Cl2,rt 98% OAc Varma. R.S.: Chatterjee, A.K.; Varma, M. Tetrahedron Lett., 1993, 34, 3207

2eq.AgNO 2 ,I 2 ,THF n.

rh

it, 30 min

rn

also works with dithianes also for protected ketones Nishide, K.; Yokota, K.; Nakamura, D.; Sumiya, T.; Node. M.: Ueda, M.; Fuji, K. Tetrahedron Lett., 1993, 34, 3425

56

Compendium of Organic Synthetic Methods, Vol 9

•Ac

Section 59

f-BuOK , THF , rt , 20 min —-_

OAc

P.T-CHO95%

Ku. Y.-Y.: Patel, R.; Sawick, D. Tetrahedron Lett., 1993, 34, 8037 DDQ H O MeOH

hv (K > 350 nm)

SPh

95% Mathew, L.; Sankararaman. S. /. Org. Chem., 1993, 58, 7576 Ph

/>-TsOH , MgS04 , PhH

'CHO

ethylene glycol , reflux , 4.5h

^^^^\

^^

IT

"

\

1 / O-—^/

97%

Lu. T.-J.: Yang, J.-F.; Sheu, L.-J. J. Org. Chem., 1995, 60, 2931 / \

\ /

HS SH . CH2d2 — CHO

CoBr2°SiO2, 3 min

also with ketones Patnev. H.K. Tetrahedron Lett., 1994, 35, 5717

,CHO

/SEt

2 EtSH , HY zeolite, CH£12

ketones can also be used

92% Kumar. P.: Reddy, R.S.; Singh, A.P.; Pandley, B. Synthesis, 1993, 67 ,CHO

ethylene glycol, TsOH microwave, 2min

ketones can also be used Moghaddam. P.M.: Sharifi, A. Synth. Commun., 1995, 25, 2457

p..

Section 60A

Protection of Aldehydes

>OMe

57

MoO2(acac)2, MeCN, 4h

OMe Kantam. M.L.: Swapna, V.; Santhi, P.L. Synth. Commun., 1995, 25, 2529

1,2-ethanediol, cat. CAN *-

Ph

CHC13 , it, overnight O

ketones can also be used Mandal, P.K.; Rov. S.C. Tetrahedron, 1995, 51, 7823

58

Compendium of Organic Synthetic Methods, Vol 9

Section 61

CHAPTER 5 PREPARATION OF ALKYLS, METHYLENES AND ARYLS This chapter lists the conversion of functional groups into methyl, ethyl, propyl, etc. as well as methylene (CH2), phenyl, etc.

SECTION 61: ,H

ALKYLS, METHYLENES AND ARYLS FROM ALKYNES l.C<#i3OCH,cat.CuCl cat. Pd(PPh)3)4, r-BuNH2 CC^Me PhMe, rt 2.PCC,CH 2 Cl 2 ,rt 3. CHC13, CSA

Ciufolini. M.A.: Weiss, T.J. Tetrahedron Lett., 1994, 35, 1127 2. 7 eq. TfOH, 22°C, 28h 2 eq. Cp(CO)3WH Luan, L.; Song, J.-S.; Bullock. R.M. J. Org. Chem., 1995, 60, 7170

33% HBr-AcOH, CH2C12 0°C -> rt

\J

72%

Masquelin, T.; Obrecht D. Tetrahedron Lett., 1994, 35, 9387

PhCsCH, 1,2-dichlorobenzene 110°C,14h zeolite HSZ-360

Ph ii

i

40% yield (49% conversion)

Sartori. G.: Bigi, F.; Pastorio, A.; Porto, C.; Arienti, A.; Maggi, R.; Moretti, N.; Gnappi, G. Tetrahedron Lett., 1995, 36, 9177

Section 61

Alkyls from Allkynes

59

,OMe Ph(H2C)3

JL

y

OMe Ph(H2C)3

J^ I

Me

°

(CH2)3Ph

Me

°

(3 : Taber. P.P.: Rahimizadeh, M. Tetrahedron Lett., 1994, 35, 9139

Ph N2

/CH2)3Ph

A

.OMe

T (CH2)3Ph

1) 71%

1. Rh(OAc)2, PhH 2. air

75% Mueller, P.H.; Kassir, J.M.; Semones, M.A.; Weingarten, M.D.; Padwa. A. Tetrahedron Lett., 1993, 34, 4285

PhO2

PhH , 37°C , 18h CO2Me

MeU2C--^y 76%

Grissom. J.W.: Klingberg, D. Tetrahedron Lett., 1995, 36, 6607

in ''

1 . TaCl5 , Zn , DME/PhH , 50°C , 2h 2. Py , THF

C5H i

3. HOC—
CsHn Takai. K.: Yamada, M.; Utimoto. K. Chem. Lett., 1995, 851

82%

60

Compendium of Organic Synthetic Methods, Vol 9

SECTION 62:

Section 64

ALKYLS, METHYLENES AND ARYLS FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES

SECTION 63:

ALKYLS, METHYLENES AND ARYLS FROM ALCOHOLS AND THIOLS

OMe OH

70%

Bijoy, P.; Subba Rao. G.S.R. Tetrahedron Lett., 1994, 35, 3341 C02Et

aH^H.TMAD.BuaP PhH,DHTD-TBP

CO2Et

CO2Et

CO2Et TMAD= Me2NCON=NCONMe2 DHTD = 4,7-dimethyl-3,5,7-hexahydro-l,2,4,7-tetrazocin-3,8-dione Tsudoda. T.: Nagaku, M.; Nagino, C.; Kawamura, Y.; Ozaki, F.; Hioki, H.; Ito, S. Tetrahedron Lett., 1995, 36, 2531 1. PhNCS , NaH 2. PhjSiH , BEt3 rt , 0.2h Oba, M.; Nishivama. K. Tetrahedron, 1994, 50, 10193

SECTION 64: ALKYLS, METHYLENES AND ARYLS FROM ALDEHYDES BER-Ni(OAc)2 , MeOH PhCH PhCHO -3 BER = borohydride exchange resin Bandgar. B.P.: Kshirsagar, S.N.; Wadgaonkar, P.P. Synth. Commun., 1995, 25, 941 Related Methods: Alkyls, Methylenes and Aryls from Ketones (Section 72)

93%

Section 65

Alkyls from Alkyls

SECTION 65: C02H

61

ALKYLS, METHYLENES AND ARYLS FROM ALKYLS, METHYLENES AND ARYLS S^**r^CO*Ei

1. e , 70°C , dioxane/5% H2SO4 »• 2. Ph-C^C-CC^Et, 220°C , 4.5h

86x77% X. ^^ CO2H ^^ ^Ph Ohno. T.: Ozaki, M.; Inagaki, A.; Hirashima, T.; Nishiguchi. I. Tetrahedron Lett., 1993, 34, 2601 5% PdCl2(PPh3)2 130°C, DMSO 4 eq. Cu , Ih N02 Shimi7.ii. N.: Kitmura, T.; Watanabe, K.; Yamaguchi, T.; Shigyo, H.; Ohta, T. Tetrahedron Lett., 1993, 34, 3421

(2

:

1) 90%

Rice. I.E.: Cai, Z.-W. J. Org. Chem., 1993, 58, 1415

,N-Cy 1.2eq.UTMP,THF 89%

2. Mel

Flippin. L.A.: Muchowski. J.M.: Carter, D.S. /. Org. Chem., 1993, 58, 2463

62

Compendium of Organic Synthetic Methods, Vol 9

Section 65

QH

«

OH

2 eq. A1C13 ,2 eq. FeCl3 50°C, Ih OMe

OMe

A0nt

Sartori. G: Maggi, R.; Bigi, F.; Grandi, M. /. Org. Chem., 1993, 58, 7271

Me OMe PhCHO, Ga2Cl4, CS2

0°C, 72h Brf (44 : 56) 77% ' Hashimoto, Y.; Hirata, K.; Kagoshima, H.; Kihara, N.; Hasegawa, M.; Saigo. K. Tetrahedron, 1993, 49, 5969

H \

ff

H

^

5 eq. H2SO4, reflux, 3.5 h

\

ff

yield based on moles of alkylating agent Chung, K.H.; Kim, J.N.; Rvu. E.K. Tetrahedron Lett., 1994, 35, 2913 1. j-BuLi.TMEDA , -90°C , THF 2. Mel, -78°C 3. H3O+ Mortier. J.: Moyroud, J.; Bennetau. B.: Cain, P.A. J. Org. Chem., 1994, 59, 4042

OAc I

Br Zndust

BocHN^ ^CO2Me

Alkylation also occurs with benzylic and ally lie halides Abood. N.A.: Nosal, R. Tetrahedron Lett., 1994, 35, 3669

97%

Section 65

Alkyls from Alkyls

63

AgBF4 , CHC13 , 0°C , 10 min

83%

Billuos. W.E.: McCord, D.J.; Maughon, B.R. Tetrahedron Lett., 1994, 35, 4493 SiMei ^

SiMe3 /)-' --MeO -<x / 3eq.VO(OEt)Cl2,CH2Cl2 \_ -75°C(2h),rt(4h) 67% Hirao. T.: Fujii, T.; Ohshiro, Y. Tetrahedron Lett., 1994, 35, 8005

MeO -6.

NEt2

l. 2. CuI«SMe2

78% Casas, R.; Cav6, C.; d'Angelo, J. Tetrahedron Lett., 1995, 36, 1039 iF2 , BF3OEt2 , CH£.\2 -78°C Matano. Y.: Yoshimune, M.; Suzuki. H. Tetrahedron Lett., 1995, 36, 7475

)H

OH Cl

Cu/Cu(C104)2 Baruah. J.B. Tetrahedron Lett., 1995, 36, 8509

I!

^

65%

64

Compendium of Organic Synthetic Methods, Vol 9

SECTION 66:

Section 68

ALKYLS, METHYLENES AND ARYLS FROM AMIDES NO ADDITIONAL EXAMPLES

SECTION 67:

ALKYLS, METHYLENES AND ARYLS FROM AMINES NO ADDITIONAL EXAMPLES

SECTION 68:

ALKYLS, METHYLENES AND ARYLS FROM ESTERS PhB(QMe)3Li, THF, 60°C , 15h ^ OCO2Et

cat. [NiCl2(dppf)]

Ph

Kobavashi. Y.: Dceda, E. J. Chem. Soc. Chem. Commun., 1994, 1789

.SCu 13%

i

NMe2 )—( , ether, 0-C

BuMgl (120 min addition)

/ PhO

Bu

quant (34% ee) PhO van Klaveren, M.; Persson, E.S.M.; del Villar, A.; Grove, D.M.; Backvall, J.-E. Tetrahedron Lett., 1995, 36, 3059

/ ( \

\ IJ V***^ ' N

o

10% Ni(acac)2,20% AlEt3 toluene, reflux, PPh3 PhB(OH)2

(2.1 : 1) 70% Trost. B.M.: Spagnol, M.D. J. Chem. Soc., Perkin Trans. L, 1995, 2083

Section 70

Alkyls from Halides

SECTION 69:

65

ALKYLS, METHYLENES AND ARYLS FROM ETHERS, EPOXIDES AND THIOETHERS

The conversion ROR —> RR' (R1 = alkyl, aryl) is included in this section.

l.Li,THF,-18°C 2. -18°C -> -70°C (air -» AT)

'O 95% Elmalak, P.: Rabinovitz. M.: Blum. J../. Heterocydic Chem., 1993, 30, 291

Li+ -BuB(allyl)3 , TMSOTf, THF, -78°C

OMe

OMe

Ph OMe

Pt 94%

Hunter. R.: Michael, J.P.; Tomlinson, G.D. Tetrahedron, 1994, 50, 871

SECTION 70:

ALKYLS, METHYLENES AND ARYLS FROM HALIDES AND SULFONATES

The replacement of halogen by alkyl or aryl groups is included in this section. For the conversion of RX -»RH (X = halogen) see Section 160 (Hydrides from Halides and Sulfonates).

OH

l

-

hv, C<5D6, (Bu3Sn)2 Br

2.12, DBU

(80:20 , Huval, C.C.; Singleton. D.A. Tetrahedron Lett., 1993, 34, 3041

\^

1. "activated" Zn , THF, it

2. 5% Pd(PPh3)4, Phi \ rt,18h \ SC^Ph SO2Ph Sakamoto. T.: Kondo, Y.; Takazawa, N.; Yamanaka, H. Tetrahedron Lett., 1993, 34, 5955

66

Compendium of Organic Synthetic Methods, Vol 9

Section 70

l.Zn*, ether, 20°C 2. H-30+

'Bu (73:27 cis:trans) Meyer, C.; Marek. I.: Courtemanche, G.; Nonnant. J.-F. Tetrahedron Lett., 1993, 34, 6053 .

SnBu3 Pd(PPh3)4, CuI-DMF 48h Levin. J.I. Tetrahedron Lett., 1993, 34, 6211

"OMe OMe MeO Moorlag, H.; Mevers. A.I. Tetrahedron Lett., 1993, 34, 6989, 6993

(90:10 S:R)

l.Zn,DMSO,THF,0°C 2. CuCN, THF, LiCl

Ph

93% O Knochel. P.: Chou, T.-S.; Jubert, C.; Rajagopal, D. /. Org. Chem., 1993, 58, 588

3 eq. PhMgCl, ether, 35°C 1.5 ZnCl2Bdioxane 10% NiCl2(dppf) Park, K.; Yuan, K.; Scott. W.J. J. Org. Chem., 1993, 58, 4866 BuMnCl, THF/NMP, rt, Ih Cahiez. G.: Marquais, S. Synlett, 1993, 45

Ph

72%

Section 70

Alkyls from Halides

67

PhCHO, -78° -> rt

w

~-

95%

.0 Barluenga. J.: Montserrat, J.M.; H6rez, J. J. Org. Chem., 1993, 58, 5976


s*Bf

1. BuLi, -40°C, hexane:THF

\

2. allyl bromide,

rt

S

/ ^

\

40%

^S

Wu, X.; Chen, T.-A.; Zhu, L.; Rieke. R.D. Tetrahedron Lett., 1993, 34, 3673 OMe

^~^/

.e',ZnBr 2 ,Ni(BF 4 ) 2 bpy 3 DMF, Bu 4 NBr, 2,2'-bipy OMe

Pd(PPh3)2Cl2 , DMF pgS ^^

83%

Sibille, S.; Ratovelomanana, V.; N6d61ec, J.Y.; Perichon, J. Synlett, 1993, 425 -2LiCl,HMPA

Ph

\/ ^

93%

Bu Arai, M.; Kawasuji, T.; Nakamura. E. Chem. Lett., 1993, 357

Cl •Cl

1. CH2=CHCH2SnBu3 , AIBN 2. HBr, hv 3. BuaSnH , AIBN

-CO

\> 51x97x51% g Zhang, W.; Hua, Y.; Hoge, G.; Dowd. P. Tetrahedron Lett., 1994, 35, 3865 'O2H

o-

1.5% KOH,NaBH 4 90°C , ACVA

\~t

Rai, R.; Collum. D B. Tetrahedron Lett., 1994, 35, 6221

. '

CO2H

68

Compendium of Organic Synthetic Methods, Vol 9

64% Hatanaka. Y.: Goda, K.; Hivama. T. Tetrahedron Lett., 1994, 35, 1279

Section 70

(58%e, R)

Tf

Zn, KI, 10% NiCl2(PPh3)2 67°C,THF,4h

>X^^^

92%

Jutand. A.: Mosleh, A. Synlett, 1993, 568

0

5% Ni(acac)2 , THF PPh3 ,10% Dibal

O

F-\

\

^-OTf

rt Quesnelle, C.A.; Familoni, O.B.; Snieckus. V. Svnlett. 1994, 349

Phi, NiBr2(bipy) , DMF Cl 54% Drandetti. M.: Sibille, S.; N6d61ec, J.-Y.; Perichon, J. Synth. Commun., 1994, 24, 145

Me2(CN)CULi2.THF -78°C -» 25°C OTf Martfnez. A.G.: Barcina, J.O.; Diez, B.R.; Subramanian, L.R. Tetrahedron, 1994, 50, 13231

Section 70

Alkyls from Halides

69

5% PdCl2(PPh3)2 , 5% TBAF THF,120°C,12h w/5%PdCl2(dppp)/TBAF/THF/20°C— \ 92% 4-(-CH2CH=CHMe) — 7.2 E/Z Hatanaka. Y.: Goda, K.; Hiyama, T. Tetrahedron Lett., 1994, 35, 6511

97%

PhB(OH)2, Pd(PPh3)4 Me02C

k \

^

OS02CF3 ff

*~ MeO2C 3 LiCl, aq. Na2CO3 Tol, EtoH Percec. V.: Bae, J.-Y.; Hill, D.H. J. Org. Chem., 1995, 60, 1060

<x \.

ff //

PhSnCl3,0.01PdCl2 \

ff

aq. KOH, 100°C, 3h

Roshchin, A.I.; Bumagin. N.A.: Beletskaya, I.P. Tetrahedron Lett., 1995, 36, 125 I

LMeZnBr,5%PdCl2(PPh3)2 DMF,12h ,CO2H

2. aq. NH4C1

Me *"

j 95%

Abarbri, M.; Parrain, J.-L.; Duchene. A. Tetrahedron Lett., 1995, 36, 2469 NaBH4,Cp2TiCl2 J

DMF, 75°C

rT

"V^\

57%

O Liu, Y.; Schwartz. J. Tetrahedron, 1995, 51, 4471

Cl

ZnCl2/SiO2,K2CO3 ^JT 61% Al 2 O 3 ,30°C,lh Kodomari. M.: Nawa, S.; Miyoshi, T. / Chem. Soc. Chem. Commun., 1995, 1895

70

Compendium of Organic Synthetic Methods, Vol 9

Section 71

B(OH)2 O2N

10% Pd(PPh3)4,10% aq. T1OH DMA, 20°C DMA = dimethylacetamide

/ —-*

77%

Anderson. J.C.: Namli, H. Synlett, 1995, 765 h

Et2Zn , 20% Lil, THF, -35°C 7.5% Ni(acac)2,18h

81% Et' Devasagayaraj, A.; Studemann, T.; Knochel. P. An$ew. Chem. Int. Ed. Engl., 1995, 34, 2723

SECTION 71:

ALKYLS, METHYLENES AND ARYLS FROM HYDRIDES

This section lists examples of the reaction of RH —> RR' (R,R' = alkyl or aryl). For the reaction C=CH -> C=C-R (R = alkyl or aryl), see Section 209 (Alkenes from Alkenes). For alkylations of ketones and esters, see Section 177 (Ketones from Ketones) and Section 113 (Esters from Esters). (CH2)6-H F3Si(—CH2)6—H , TB AF, THF 5% Pd(PPh3)4,100°C

61%

Matsuhashi, H.; Juroboshi, M.; Hatanaka, Y.; Hivama. T. Tetrahedron Lett., 1994, 35, 6507 °2H

1. s-BuLi/TMEDA-THF -98°C -» -78°C 2. Mel 3.H +

'Cl "^ "Cl Bennetau. B.: Mortier. J.: Moyroud, J.; Guesnet, J.-L. J. Chem Soc., Perkin Trans. L, 1995, 1265

Section 72

Alky Is from Ketones

71

Me

,Si(OEt)3 , toluene, 2h

^•^

^\.

Me

93% 4% Ru(H)2(CO)(PPh3)3 reflux ^f ^^ ^Si(OEt)3 Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N.; Murai. S. Bull. Chem. Soc. Jpn., 1995, 68, 62

SECTION 72:

ALKYLS, METHYLENES AND ARYLS FROM KETONES

The conversions R2C=O -> R-R, R2CH2, RiCHR', etc. are listed in this section. !

°2Et

l.TsNHNH2 2. NaBHsCN. ZnCl2

C.O2Et +

(3.5 : Taber. D.F.: Wang, Y.; Stachel, S.J. Tetrahedron Lett., 1993, 34, 6209

1) 66%

Me3Al-TMSOSO2CF3 CH2C12,0°C -> 25°C, 15h

95%

-" -

o

Kim. C.U.: Misco, P.F.; Luh, B.Y.; Mansuri, M.M. Tetrahedron Lett., 1994, 35, 3017 C

°2H l.Mel.KOH.DMSO rt,5h

MeCT

^

O

2. H2O

MeCT Yli-Kauhaluoma, J.T.; Janda. K.D. Tetrahedron Lett., 1994, 35, 4509

6NaOEt,2I 2

,

EtOH, -78°C Heede. S.G.: Kassim, A.M.; Ingram, A.I. Tetrahedron Lett., 1995, 36, 8395

^*^

,

93%

^

72

Compendium of Organic Synthetic Methods, Vol 9

Section 74A

, r-BuOK 20% MeOH , rt, Id

O Coe. J.W.: Vetelino, M.G.; Kemp, D.S. Tetrahedron Lett., 1994, 35, 6627

1. MeMgBr 2. VCl2(uneda)2

50% Kataoka, Y.; Makihira, I.; Akiyama, H.; Tani. K. Tetrahedron Lett., 1995, 36, 6495

SECTION 73

ALKYLS, METHYLENES AND ARYLS FROM NITRILES NO ADDITIONAL EXAMPLES

SECTION 74:

ALKYLS, METHYLENES AND ARYLS FROM ALKENES

The following reaction types are included in this section: A. B. C. D. E. F.

Hydrogenation of Alkenes (and Aryls) Formation of Aryls Alkylations and Arylations of Alkenes Conjugate Reduction of Conjugated Aldehydes, Ketones, Acids, Esters and Nitriles Conjugate Alkylations Cyclopropanations, including halocyclopropanations

SECTION 74A: Hydrogenation of Alkenes (and Aryls) Reduction of aryls to dienes are listed in Section 377 (Alkene-Alkene). [ (f-Bu2Ph)PdPf-Bu]2 / 02 THF,H 2 Cho, I.S.; Alper. H. J. Org. Chem., 1994, 59, 4027

S02ph

46%

Section 74A

Hydrogenation of Alkenes

"colloidal palladium"

73

*rT " vx"

>99%

"colloidal palladium" = [TMS(OSiHMe)nOTMS]Pd(hfacac)2 Fowley, L.A.; Michos, D.; Luo, X.-L.; Crabtree. R.H. Tetrahedron Lett., 1993, 34, 3075 chiral catalyst, H 2 ,65°C ph-

-^

Ph

Ph-

91% (>99% ee) Broene, R.D.; Buchwald. S.L. J. Am Chem. Soc., 1993, 115, 12569

RuCl 3 , TOA 99%

TOA = trioctylamine

(cis/trans = 1.5) Fache, F.; Lehuede, S.; LeMaire. M. Tetrahedron Lett., 1995, 36, 885 Ph

[ (r-Bu2PH)Pd(Pf-Bu)2]2, H 2 ,0 2 THF/CH2C12, 6h

O Cho, I.S.; Lee, B.; Alper. H. Tetrahedron Lett., 1995, 36, 6009

OH

«

aq. Ba(OH)2, NiAl(Raney alloy) ^60°C, Ih

54%

Br ^^ Br Tsukinoki, T.; Kakinami, T.; lida, Y.; Ueno, M.; Ueno, Y.; Mashimo, T.; Tsuzuki, H.; Tashiro. M. /. Chem. Soc. Chem. Commun., 1995, 209

H 2 ,[W 2 (OCH 2 f-Bu) 6 (Py) 2 ]

^^

Barry, J.T.; Chisholm. M.H. J. Chem. Soc. Chem. Commun., 1995, 1599

no yield

74

Compendium of Organic Synthetic Methods, Vol 9

Section 74B

SECTION 74B: Formation of Aryls OMe .=/

OMe

OMe QMe

OTf

LiCl , CuBr , inhibitor Pd(PPh3)4 , dioxane , reflux OMe Saa. J.M.: Martorell, G. J. Org. Chem., 1993, 58, 1963

x

-\ OMe

*-y 93%

170°C, C6H4C12, 2h 1,4-CHP CO2Me Grissom. J.W.: Calkins, T.L.; McMillen, H.A. J. Org. Chem., 1993, 58, 6556 50 atm CO, PdCl2(PPh3)2, NEt3

'OAc

PhH, 140°C, 3h

OAc 69% Ishii, Y.; Gao, C.; Xu, W.-X.; Iwasaki, M.; HidaLJ/L/ Org. Chem., 1993, 58, 6818

/

=

HSiMe2r-Bu, C) (50 atm) Rus(CO)i2/PCy3,140°C, 20h

/^~^5:^^OSiMe2r-Bu OSiMe^-Bu

45% Chatani, N.; Fukumoto, Y.; Ida, T.; Murai. S. J. Am. Chem. Soc., 1993, 115, 11614

A

PhOH, PhMe, 180°C

<=~~

52%

Danheiser. R.L.: Gould, A.E.; de la Pradilla, R.F.; Helgason, A.L. J. Org. Chem., 1994, 59, 5514

Section 74B

Formation of Aryls

75

20% Ni(0)-PPh3, HOCH N—Ts

N—Ts

THF,23°C,12h

'^^

91%

Sato, Y.; Nishimata, T.; Mori. M. J. Org. Chem., 1994, 59, 6133 l.PhNH2 2. Pd(OAc)2, MeCN PhCHO 3. BuLi/PPh3/ Br4. 2% HC1 Rama Rao. A.V.: Reddy, K.L.; Reddy, M.M. Tetrahedron Lett., 1994, 35, 5039 OH 1.5

^ss=^

\

^

0.1SnCl4,0°C 1.5 (MeO)3SiMe3 1QM.

^^

^^X.

'Si(iPr)3

Angle. S.R.: Boyce, J.P. Tetrahedron Lett., 1994, 35, 6461

Me

r-BuOOCOPh, Cu(OAc)2 CuBr,PhH,80°C,8.5h BocHN 56%

Tavares, F.; Mevers. A.I. Tetrahedron Lett., 1994, 35, 6803 N-OH

, Bn

5% Pd/C, diethylene glycol 188°C , diethyl ether, 45 min

NH2

AT Ar = 4-methoxyphenyl ^^^ Ar Matsumoto. M.: Tomizuka, J.; Suzuki, M. Synth. Commun., 1994, 24, 1441

76

Compendium of Organic Synthetic Methods, Vol 9

Section 74C

SECTION 74C: Alkylations and Arylations of Alkenes MeQ

DMe

MeCj

OMe

O

2 BF3»OEt2 25°C

Maietich. G.: Zhang, Y.; Feltman, T.L. Tetrahedron Lett., 1993, 34, 441 Maietich. G.: Zhang, Y.; Feltman, T.L.; Duncan Jr., S. Tetrahedron Lett., 1993, 34, 445 -Ar

P£

l.PhLi,

/ MeO

Ph

( OMe

Toluene, -45°C , 18h 2. LiEt3BH 3. MeOH 4. NaBH4 AT = 2,6-di-f-Bu-4-OMephenyl Tomioka. K.: Shindo, M.; Koga, K. Tetrahedron Lett., 1993, 34, 681

1

-^

DMF , BU4NC1 , Id

O

10%Pd(OAc)2,3iPr2NEt 55,34 £-z 5HCO2Na Larock. R C. : Ding, S. Tetrahedron Lett., 1993, 34, 979

^S..x

i

OH

cat. Pd(OAc)2 , Ag2Cp3 DMF , 45°C , overnight ip

I ^1 Jefferv. T. Tetrahedron Lett., 1993, 34, 1133

CO2Me

99%

Me

NH2

Section 74C

Alkylation of Alkenes

77

I.EtZnCI

_ \ 2. BuZnCl.DMF r,,/' \^^^^•/"Yf-I /"\i_r 13 U 5% Cl2Pd(PPh3)2 2BuLi,5h Negishi. E.: Ay, M.; Gulevich, Y.V.; Noda, Y. Tetrahedron Lett., 1993, 34, 1437

^O^

\

/

0.1 Pd(OAc)2 ,40°C 0.2 AsPh 3 , MeCN/H2O lOh Zhang, H-C.; Brakta, M.; Daves Jr.. G.D. Tetrahedron Lett., 1993, 34, 1571

OTf

Q. IL /

, 30°C, 91h

Pd(R-BINAP)2 , PhH Proton Sponge

87%

||

<*'R

Qzawa. F.: Kobatake, T.; Havashi. T. Tetrahedron Lett., 1993, 34, 2505

\

Pror

?

\. n 3 SnBu

C
\

p 52%

Pror

V.TT CsHn

Kinnev. W.A. Tetrahedron Lett., 1993, 34, 2715

y=i

PhBr, Tol, 2% Pd(PPh3)4

;==i

BusSn ' NH2 *" Ph ^ Corriu. RJ.R: Geng, B.: Moreau. J.J.E. .7. Org. Chem., 1993, 58, 1443 C8H17 BU3Sn

MB '

^^ l.Me2SCHC02Et

B(C#i3)2

— ^ ^ > ——

NH2

C8H17

Deng. M.-Z.: Li, N.-S.; Huang. Y.-Z. J. Org. Chem., 1993, 58, 1949

\

CO2Et

78

Compendium of Organic Synthetic Methods, Vol 9

Section 74C

NHCy

NHCy

BusSnH, AIBN

MeO

Br

Righv. J.H.: Qabar, M.N. 7. Org. Chem., 1993, 58, 4473

1. S U

" 1. PdCl2 , LiCl , THF ' 0°C -» 25°C 2. aq. NH4C1 2. PhHgCl , 02

O 60% (74:26 E:Z)

Larock. R.C.: Ding, S. J. Org. Chem., 1993, 58, 2081 (CH2)8C02Me

PhOTf , Pd(PPh3)4 , 85°C K3?O4, dioxane

87%

Oh-e, T.: Mivaura. N.: Suzuki. A. 7 Org. Chem., 1993, 58, 2201 1. 2 Et2Zn , 1.5% PdCl2(dppf), THF 2.CuCN'2LiCl

p_

/

3. ^Br

^

73%

Stadmuller, H.; Lentz, R.; Tucker, C.E.; Stiidemann, T.; Dfirner, W.; Knochel. P. 7 Am Chem. Soc., 1993, 115, 7027 3 eq. EtMgBr, Cp2ZrCl2

THF, rt, 6h

\

Suzuki, N.; Kondakov, D.Y.; Takahashi. T. 7. Am Chem. Soc., 1993, 115, 8485

70%

Section 74C

Alkylationof Alkenes

N2+BF4

79

,CO2Et ,EtOH

2% Pd(OAc)2,60°C, Ih

MeO' MeO" Sengupta. S.: Bhattacharyya, S. J. Chem. Soc., Perkin Trans. 1., 1993, 1943 5 eq. MeMgBr 0.05 PdCl2(PPh3)2

°H

= Cl Hoffmann. R.W.: Giesen, V.; Fuest, M. Liebigs Ann. Chem., 1993, 629 e., DMF, /

\

47%

Ni(teta)(ClO4)2 Ozaki. S.: Horiguchi, I.; Matsushita, H.; Ohmori, H. Tetrahedron Lett., 1994, 35, 725 LDA, TMS-C1 THF, -78°C Et Wright. S.W. Tetrahedron Lett., 1994, 35, 1841

:O2Me

Et

93%

Phi, BU4NHSO4, aq. MeOH 5% [Pd(OAc)2/2 PPh3]

CO2Me „/ Pti

96%

Heck reaction in aqueous media

Jefferv. T. Tetrahedron Lett., 1994, 35, 3051 Phi, SmI2/THF, 15 min DMSO

0 Nazareno, M.A.; Rossi. R.A. Tetrahedron Lett., 1994, 35, 5185

Ph

47%

80

Compendium of Organic Synthetic Methods, Vol 9

Section 74C

Ph Pd(OAc)2, Bu 3 P, 3h K2CO3 , DMF, 80°C Phl

MeHNCOO

MeHNCOO' quant. (78 6) Ono, K.; Fugami, K.; Tanaka, S.; Tamaru. Y. Tetrahedron Lett., 1994, 35, 4133

70% Majetich. G.: Zhang, Y.; Liu, S. Tetrahedron Lett., 1994, 35, 4887 SnBu3 F

Pd(PPh3)4, THF, 65°C , Ih

O'

Matthews, D.P.; Waid, P.P.; Sabol. J.S.: McCarthy. J.R. Tetrahedron Lett., 1994, 35, 5177 TfO

=\

•OMe

\

SnBu3

(/

\>

QMe

70% Badone. P.: Cardamone, R.; Guzzi, U. Tetrahedron Lett., 1994, 35, 5477 SnBu3

°

5% Pd2(dba)3 , 20% AsPh3 2. 5% TFA, CH2C12 = Rink amide resin

Peshnande. M.S. Tetrahedron Lett., 1994, 35, 5613

Section 74C

Alkylation of Alkenes

81

2eq.Me3SiCH2Mga 5%NiCl2(PPh3)2,DME reflux, 1.5h Hevesi. L.: Hermans, B.; Allard, C. Tetrahedron Lett., 1994, 35, 6729

// //ff

^ \ ^

1. 0.3 Ti3-C3H5PdCl)2 , HSiPh2F 0.6 o'-diphenylphosphinobinaphthol derivative *20°C , lOh 2. MeLi

Ph,

Me ' _.„. _ _ SlPh Me ' 96% (66% ee, S) Hatanaka. Y.: Goda, K.; Yamashita, F.; Hiyama, T. Tetrahedron Lett., 1994, 35, 7981

Ph

NC

NH2

Mn(OAc)3 , CuOAc ultrasound, 4h

CN

.

47%

Bosman, C.; D'Annibale. A.: Resta, S.; Trogolo. C. Tetrahedron Lett., 1994, 35, 8049 f —\ I V-OTf ^^/

Bu4N+(Ph3SnF2)-,THF f^\ -Pd(PPh3)4 , reflux , 30 min ^*#

I

81% Martinez. A.G.: Barcina, J.O.; Cerezo, A. de F.; Subramanian, L.R. Synlett, 1994, 1047

10%ZrCl2(TlC5H2),1.5BuMgCl

Takahashi. T.: Kotora, M.; Kasai, K. J. Chem. Soc. Chem. Commun., 1994, 2693 SiMe3 l.BuLi,THF,-70°C 2. ZnBr2 , -70°C -> 20°C OMEM OMEM

V-Ph

82

Compendium of Organic Synthetic Methods, Vol 9

Section 74C

SiE, tridecane , di-f-Bu hyponitrite

65% Dang, H.-S.; Roberts. B.P. Tetrahedron Lett., 1995, 36, 2875 Br

^.

PhSnCl3,aq.KOH,3%PdCl2

Ph

k

COOH

"^

COOH

83% Rai, R.; Aubrecht, K.B.; Collum. D.B. Tetrahedron Lett., 1995, 36, 3169

.1 B U3 SnH,Si0 2 CH2C12 , it , Id

=0 tandem radical cylization-Diels-Alder Journet, M.; Malacria. M. J. Org. Chem., 1995, 60, 6885

CO2Et

/

Mg , MeOH, rt, 2h

~\A_ N

Et

CO2Et

/

CO2Et

/"^l

CO2Et

~ (87 : Chavan. S.P.: Ethiraj, K.S. Tetrahedron Lett., 1995, 36, 2281

>

CO2Et

13) 90%

)Me

OMe BF3^OEt2, CeHn, reflux , 2h

O' 56% Maietich. G.: Liu, S.; Siesel, D. Tetrahedron Lett., 1995, 36, 4749

Section 74C

Alkylation of Alkenes

83

Pd(OAc)2,20% Bu3P Phi, DMF, 100°C , 1.5h

,„, H0 ''**,,/ **OH

O

85% Kang. S.-K.: Jung, K.-Y.; Park, C.-H.; Namkoong, E.-Y.; Kim, T.-H. Tetrahedron Lett., 1995, 36, 6287

(95 Zhang, W.; Dowd. P. Tetrahedron Lett., 1995, 36, 8539 H

2PPh3,toluene/PhH 2 DEAD

^y^

,S02Ph

PhO^

i H

S02Ph

95%

Yu, J.; Cho, H.S.; Falck. J.R. Tetrahedron Lett., 1995, 36, 8577 ,SiEt3 , PhMe, reflux 5% RuH2(CO)(PPh3)3

\

^^^

—"x^

94%

Trost. B.M.: Imi, K.; Davies, I.W. J. Am. Chem. Soc., 1995, 117, 5371 . Me3Al, 8% Cl2ZrCp2, DCE, 22°C

2.02 92% (74% ee)

Kondakov, D.Y.; Negishi. E../. Am. Chem. Soc., 1995, 117, 10771

'SiEt3

84

Compendium of Organic Synthetic Methods, Vol 9

Section 74D

CO2Et ,5%Pdcl2(PPh3)2 . . 3LiCl,DMF,110°C N Draper, T.L.; Bailev. T.R. Svnlett. 1995, 157

o

=*

Si(OEt)3 , toluene, 135°C

Ru(H)2(CO)(PPh3)2, 2d

50% Kakiuchi, F.; Tanaka, Y.; Sato, T.; Chatani, N.; Murai. S. Chem. Lett., 1995, 679 1.BC13,CH2C12,00C SiMe

3

2. catechol, PhH 3. PhBr, Pd(PPh3)4, NaOH Farinola, G.M.; Fiandanese, V.; Mazzone, L.; Naso. F. J. Chem. Soc. Chem. Commun., 1995 2523 REVIEW: "Recent Developments and New Perspectives In The Heck Reaction," Cabri. W.: Candiani, T. Accts. Chem. Res., 1995, 28, 2

SECTION 74D:

Conjugate Reduction of a,p-Unsaturated Carbonyl Compounds and Nitrites 2% [Pd(Pr-Bu)(PHr-Bu2)]2 O 2 ,H 2 (10psi) THF,18h glass autoclave

*

'

Me Sommovigo, M.; Alper. H.Tetrahedron Lett., 1993, 34, 59

CO (1 atm) , NEt3 , 30°C Joh. T.: Fujiwara, K.; Takahashi, S. Bull. Chem. Soc. Jpn., 1993, 66, 978

90%

Section 74D

Conjugate Reduction

85

PhSiH3 , 20°C , 16h Mo complex

(62

38) 95% conversion

:

Schmidt. T. Tetrahedron Lett., 1994, 35, 3513 NaHTe.EtOH Ph< TTT ^^ "CHO rt 5h ' Yamashita. M.: Tanaka, Y.; Arita, A.; Nishida, M. J. Org. Chem., 1994, 59, 3500

'CHO

CO2Me

TFA-Et3SiH , 30 min

-e

-78°C -» 0°C

>98%

,CO2Me /

various protonic and Lewis acids used Zhao, Y.; Quavle. P.: Keo, E.A. Tetrahedron Lett., 1994, 35, 4179

NH4+ HCO2-, Pd-C C:HO

25°C,4h

•"

^

CHO 92%

Ranu. B.C.: Sarkar, A. Tetrahedron Lett., 1994, 35, 8649 VT^ .NO2

Bakers yeast, 31°C

^^ Ph 3d Takeshita. M.: Yoshida, S.; Kohno, Y. Heterocycles, 1994, 37, 553

limonene , 10% Pd/C , reflux

.N02

^\ /^°

43%

quant>

von Holleben. M.L.: Zucolotto, M.; Zini, C.A.; Oliveira, E.R. Tetrahedron, 1994, 50, 973

86

Compendium of Organic Synthetic Methods, Vol 9

Section 74E

O

I, aq. dioxane, 50°C , Ih PhJ

^

^

^ Ph'

*CHO

^

^^

^^

^^ CHO

selective reduction of conjugated carbonyl C=C units Dhillon. R.S.: Singh, R.P.; Kaur, D. Tetrahedron Lett., 1995, 36, 1107

Sm , I2 , MeOH , 1 min *•

Ph^^^ 97%

Yanada. R.: Bessho, K.; Yanada, K. Synlett, 1995, 443 ,CO2Me

BER-CuSO4, MeOH, rt

BER = borohydride exchange

resin

^

Sim, T.B.: Yoon. N.M. Svnlett. 1995, 726 NaBH4-BiCl3,95% EtOH 'CO2Et Ren, P.-D.; Pan, S.-F.; Dong, T.-W.; Wu. S.-H. Svnth. Commun., 1995, 25, 3395 Bakers yeast PIT

^V

^

Ph'

42% (71% ee) Kawai. Y.: Saitou, K.; Hida, K.; Ohno, A. Tetrahedron Asymmetry, 1995, 6, 2143

SECTION 74E: Conjugate Alkylations )SiMe3 alumina-ZnC!2,0°C , 5 min

78%

Ranu. B.C.: Saha, M.; Bhar, S. Tetrahedron Lett., 1993, 34, 1989

Section 74E

Conjugate Alkylations

87

1) 81%

(15 : Corev. E.J.: Houpis, I.N. Tetrahedron Lett., 1993, 34, 2421

l.PhMgBr,CuBr-SMe 2 6 X >\

*•

2. NBS , THF , -78°C

ii

O O Li, G.; Jarosinski, M.A.; Hrubv. V.J. Tetrahedron Lett., 1993, 34, 2565

A 0

Ph£uLi , THF , -78°C

20%

v.

fc

+ TMSC1 + TMSCN

81% 83%

. \ ^ Ph

Linshutz. B.H.: James, B. Tetrahedron Lett., 1993, 34, 6689

0.05 (Bu3Sn)2 6eq.PhSCH(OMe>2 0.3 M PhH , hv (sunlamp)

Me( (8:1 trans:cis)

Keck. G.E.: Kordik, C.P. Tetrahedron Lett., 1993, 34, 6875

[

Me(Boc)NCH2SnBu3/J-BuLi TMEDA , CuCN , THF

™SC1 Dieter. R.K.: Alexander, C.W. Synlett, 1993, 407

•

•

.NMeBoc

88

Compendium of Organic Synthetic Methods, Vol 9

Section 74E

71% (25%ee) Eu(tfc)3 = [tris-(3-trifluoromethylhydroxymethylene)-d-camphorato] europium (III) Bonadies, F.; Lattanzi, A.; Orelli, L.R.; Resci, S.; Screttri. A. Tetrahedron Lett., 1993, 34, 7649

1. BnOCH2CH2OCH/Cp2Zr(H)Cl 2. MeLi, Me2Cu(CN)Li2

81%

Lipshutz. B.H.: Wood, M.R. /. Am. Chem. Soc., 1993, 115, 12625 O

1. Ni(acac)2 2

,SiMe3 ZnCl

80%

Eshelby, J.J.; Crowley, P.J.; Parsons. PJ. Synlett, 1993, 279

J -T

CO2Et

-. Me - -2CuLi»LiI - - - -

Me Me \/ \=/ C02Et

..

MM

2.MeOTf Bu

71%

Amdt, S.; Handke, G.; Krause. N. Chem. Ber., 1993, 126, 251 1 . f-BuBr , Cr(en)2+2 , DMF , 4h 78% 2 H

- 2O

en = ethylene diamine Tashtoush, H.I.; Sustmann. R. Chem. Ber., 1993, 126, 1759

SO2Ph

Section 74E

Conjugate Alkylations

89

, cat. Pd(OAc)2 AgOAc, AcOH, 25°C

ph

41%

Cho, C.S.; Tanabe, K.: Uemura. S. Tetrahedron Lett., 1994, 35, 1275

TBSO- IT

>-.C02Me

3eq. SmI2,THF,-78°C

Enholm. EJ.t Trivellas, A. Tetrahedron Lett., 1994, 35, 1627 cat. Pd(OAc)2, NaOAc, Id cat. SbCl3, AcOH, 25°C O Ph Cho, C.S.; Motofusa, S.: Uemura. S. Tetrahedron Lett., 1994, 35, 1739

O

MeO, 'CO2Me

3eq.Me 3 SiSnBu 3 ,2eq.CsF DMF,rt,lh

^^

'CO2Me

Br Sato, H.; Isono, N.; Okamura, K.; Date, T.; Mori. M. Tetrahedron Lett., 1994, 35, 2035

MeTi(OiPr)4MgCl , THF Ni(acac)2, -15°C ->• rt O" 85% Flemming. S.: Kabbara, J.; Nickisch, K.; Neh, H.; Westermann, J. Tetrahedron Lett., 1994, 35, 6075

90

Compendium of Organic Synthetic Methods, Vol 9

Section 74E

f-BuHgCl, Et3SiH , DMSO c02Et

dark,hv(sunlamp)

E

•jcop iiu -35 C , llh

„

3

93%

Russell. G.A.: Shi, B.Z. Tetrahedron Lett., 1994, 35, 3841

\-'

iPrCHO,LiNO3,aq.MeCN

<

=<

\

//

J -/

"/vX 34%

C02Me

Shono. T.: Soejima, T.; Takigawa, K.; Yamaguchi, Y.; Maekawa, H.; Kashimura. S. Tetrahedron Lett., 1994, 35, 4161 c

°2'-Bu

.C02r-Bu l.BuLi.THF -100°C -» 30°C 2. H-20

I

I

70% +

other isomers

Cooke Jr.. M.P.: Gopal, D. Tetrahedron Lett., 1994, 35, 2837

PhCHO, Ph2CO 69%

hv O

Kraus. G.A.: Liu, P. Tetrahedron Lett., 1994, 35, 7723

MeMgCl, CeCl3 , THF \\

\

\\

93%

Bartoli. G.: Bosco, M.; Sambri, L.; Marcantoni, E. Tetrahedron Lett., 1994, 35, 8651

Section 74E

Conjugate Alkylations

91

hv, PPh3 , DCA, DMF

O (70

:

/

30)

55%

Pandev. G.: Hajra, S.; Ghorai, M.K. Tetrahedron Lett., 1994, 35, 7837 •CO2Me

C5Hi

C*Hir^

(1 : 1) 54% Miura, K.; Itoh, D.; Hondo, T.; Hosomi. A. Tetrahedron Lett., 1994, 35, 9605 Q

BuOCH , PhCsCSnEt3 , Me^iCl Ni(acac)2, Dibal, THF, rt, 2h Ph'

Ikeda, S.; Sato. Y. J. Am. Chem. Soc., 1994, 116, 5975

;HO :HO

AlMe3/hexane/THF

^. Bu

5% CuBr, 0°C , 2h 94% (93:7 1,4:1,2) Kabbara. J.: Hemming, S.; Nickisch, K.; Neh, H.; Westermann, J. Synlett, 1994, 679 Et2Zn , MeCN, 1.5% NiCl2 , -30°C Ph

^

Ph 3o%chiraipyrrolidme 75% (82% ee, S)

Asami. M.: Usui, K.; Higuchi, S.; Inoue, S. Chem. Lett., 1994, 297

92

Compendium of Organic Synthetic Methods, Vol 9

Ph—^=

Section 74E

Li j v^ii2^-''2

I

I

99%

Al(OAr)3, -78°C, Ih AT = 2,5-diphenyIphenyl Maruoka, K.; Shimada, I.; Imoto, H.; Yamamoto. H. Svnlett. 1994, 519

HSiPhMe2, toluene, 110°C

^

PhMe2Si I \ ^^

[Rh2(OAc)4]

N

Bn Murai. T.r Oda, T.; Kimura, F.; Onishi, H.; Kanda, T.; Kato. S. J. Chem. Soc. Chem. Commun., 1994, 2143

87%

1 . PhMe2SiLi , Me2Zn , THF/toluene , 0°C 2.aq.NH4Cl CO2Me 98% 73% using cuprate Crump, R.A.N.C.; Fleming. I.: Urch, CJ. J. Chem. Soc., Perkin Trans. 1., 1994, 701

5% CuBr, THF, TMSC1, 4h A1MC3 ,10% solution in hexane

Kabbara. J.: Flemming, S.; Nickisch, K.; Neh, H.; Westermann, J. Chem. Ber., 1994, 127, 1489

r-Bu

\

(r-Bu)2Cu(CN)Li2

CO2Et Gerold, A.; Krause. N. Chem. Ber., 1994, 127, 1547

Section 74E

Conjugate Alkylations

93

o '

, DME, 0.3h

N

CC^Et

Bonadies. F.: Forcellese, ML.; Locati, L.; Screttri, A.; Scolamiero, C. Gazz. Chim. Ital., 1994, 124, 467 . NiBr2 , e"

C02Et

PI

-

63%

3 H2O , DMF-Py , 80°C Bii4NBr , BU4NI Condon-Guegnot. S.: Ldonel, E.; N6d61ec, J.-Y.; Pdrichon, J. / Org. Chem., 1995, 60, 7684 OSiMe3

O=<

=O

5 M LiClO4, ether

Sarawathy, V.G.; Sankararaman. S. 7. Org. Chem., 1995, 60, 5024

r-B

f-BuZnBr, THF/pentane, -3°C

71%

2TMSCl,1.5BF3OEt2 Hanson, M.V.; Rieke. R.D. 7. Am. Chem. Soc., 1995, 117, 10775

n

N

\

/ -'tff

x

.

.

CH2Cl2/hexane/THF

^

\

/ 89% (45:1) \ CHPh2 ''CHPh2 Sibi. M.P.: Jasperse, C.P.; Ji, J. J. Am. Chem. Soc., 1995, 117, 10779 neat A1(C3H7)3 , 5% CuBr

xx. X

PIT

76% Kabhara. J.: Hemming, S.; Nickisch, K.; Neh, H.; Westennann, J. Tetrahedron, 1995, 51, 743

94

Compendium of Organic Synthetic Methods, Vol 9

Section 74F

CO2Me 2. LTA, PhH, heat CO2Me 98x25% Barton, D.H.R.; Chern, C.-Y.; Jaszberenvi. J.Cs. Tetrahedron, 1995, 51, 1867 O SnBu,

O

•'«O , ether Zn(OTf)2, -78°C

Ph

61%(80%ee; 10:90 R:S) Wu, J.H.; Radinov, R.; Porter. N.A. J. Am. Chem. Soc., 1995, 117, 11029 REVIEW: "Intramolecular Michael and Anti-Michael Additions to Carbon-Carbon Triple Bonds," Rudorf, W.-D.; Schwarz, R. Synlett, 1993, 341

SECTION 74F:

Cyclopropanations, including Halocyclopropanations ,SO2Ph

-CH(SOMe)2, DMSO

"

99%

20°C, 15 min Backvall. J-E.: Lofstom, C.; Juntunen, S.K. Tetrahedron Lett., 1993, 34, 2007 N2CHCO2f-Bu, CuOTF-biarylamine ligand

?K

p

*CO2r-Bu (86

.

„«. „

92% ee Ito, K.; Katsuki. T. Tetrahedron Lett., 1993, 34, 2661

*• EtOH, 60-70°C, 15h Hu. C.-M.: Chen, J. Tetrahedron Lett., 1993, 34, 5957

"

C2F

•

CO2r-Bu \A\ AH I

TiOL / J fO

\/ ^CO2Et

Section 74F

Cyclopropanations

PhJ1 \

95

e—Li

THF , 0°-»20°C

Kreif. A.: Dubois, P. Tetrahedron Lett., 1993, 34, 2691 I) O

P

O

, LiBr , rt

Bu3SnN(Et)CO2Me , DCE

78%

(93:7 l,2-trans:cis) Shibata. I: Mori, Y.; Yamasaki, H.; Baba, A.; Matsuda, H. Tetrahedron Lett., 1993, 34, 6567 h

/n

bis-Kb catalyst , styrene

-

If t-

CO2Me

Aiiiiiiini'

CO2Me

MeO 63% 90%ee Davies. H.M.L.: Hutcheson, O.K. Tetrahedron Lett., 1993, 34, 7243 l.NBS,DMSO,5min 2. KOH, 5h 3. IMAcOH

,^

,

. :1 as:trans)

Dechoux, L.; Ebel, M.; Jung, L.; Stembach. J.F. Tetrahedron Lett., 1993, 34, 7405 O OEt O

10% Pd(PPh3)4 , DMF, 7h

6 99% Ogoshi, S.; Morimoto, T.; Nishio, K.; Ohe, K.; Murai. S. J. Org. Chem., 1993, 58, 9

96

Compendium of Organic Synthetic Methods, Vol 9

Section 74F

>TL c

/Vx^o

- I °°

.^A (97 : 3) 84% Ph.— Davies. H.M.L.: Huby, N.J.S.; Cantrell Jr., W.R.; Olive, J.L. J. Am. Chem. Soc., 1993, 115, 9468

||

CrCl2 - DMF, 3h

Buu-^~^CHO --- CHO

/\ Bii^ Bu

"OH 32% Montgomery, D.; Reynolds, K.; Stevenson. P. J. Chem. Soc. Chem. Commun., 1993, 363

LiCH(SPh)SO2Ph, THF SPh

-78°C ^ 0°C

^X ^I

\ *SPh

81% BaUey, P.L.; Hewkin, C.T.; Clegg, W.; Jackson. R.F.W. J. Chem. Soc., Perkin Trans. L, 1993, 577

¥e

© Ph

Na+-CH(CO2Me)2,THF-HMPA

..

xCO2Me

-70°C ^ 0°C , 3h 63%

Watanabe, Y.; Ueno, Y.; Tom. T. Bull. Chem. Soc. Jpn., 1993, 66, 2042 CH 2 I 2 ,Zn,Et 2 0 40°C , 8h Pb, Me3SiCl Takai. K.: Kakiuchi, T.: Utimoto. K. / Org. Chem., 1994, 59, 2671

97%

Section 74F

Cyclopropanations

97

(Bu3Sn)2, hv

50%

PhH, lOh MeO^

"CO2Me

~CO2Me Denis, R.C.: Gravel. D. Tetrahedron Lett., 1994, 35, 4531

(2.7 OH

2eq.Et 2 Zn,CH 2 I 2 CH2Cl2-hexane, -20°C

a

BU3Sn, A H \/\^

JNHSU2<-6H4p-INU2

/

\

„„

NHS02^6H^-N02 86% ^ (2S.3R), 94% Imai, N.; Sakamoto, K.; Takahashi, H.; Kobavashi. S. Tetrahedron Lett., 1994, 35, 7045 1. PhCHN2 2. PhCH=CH2, rt, 12h

Cpx /"^ OC—Fe—Q OC v*«—

Ph

80% (96:4 cis:trans) Seitz, WJ.; Hossain. M.M. Tetrahedron Lett., 1994, 35, 7561 Me2NOCl

"Ph

#CONMe2

Bu

2.2.2Zn(CH2I)2 >95%(29:1) Charette. A.B.: Juteau, H. /. Am. Chem. Soc., 1994, 116, 2651 Et2Zn , CH2I2 , CH2C12 hexane ,-20°C H

"

SO2Ph B— iBu

SO2Ph Imai, N.; Takahashi, H.; Kobavashi. S. Chem. Lett., 1994, 177

quant. (76% ee)

98

Compendium of Organic Synthetic Methods, Vol 9

Section 74F

Ph Ph 0

Br Bu2Te

Cs£03 , 70°C DME , trace water 8)93% Huanp. Y.-7.: Tang, Y.; Zhou, Z.-L.; Xia, W.; Shi, L.-P. J. Chem. Soc., Perkin Trans. L, 1994, 893

3-pentanone/LDA, THF SO2Ph

3d

62% Ericsson, A.M.; Plobeck, N.A.; Backvall. J.-E. Acta Chem. Scand. B., 1994, 48, 252

57%

Motherwell. W.B.: Roberts, L.R. Tetrahedron Lett., 1995, 36, 1121 2 Ti(OiPr)44iPrMgBr

H< OH

-45°C -» 0°C

93% (58:42 trans:cis) Kasatkin, A.; Sato. F. Tetrahedron Lett., 1995, 36, 6079 1. Zn(CH2I)2

,OH

2

- -78°C -* -20°C 3.TH 90%

Charette. A.B.: Brochu, C. J. Am. Chem. Soc., 1995, 117, 11367

Section 75

Alkyls from Misc.

N2

99

5% semi-corrin Cu complex , DCE 23°C

57% (95% ee)

Piqu6, C; FShndrich, B.; Pfaltz. A. Svnlett. 1995, 491 )H

OH

1.SOC12,CC14, reflux 2. NaIO4 , 0.1 RuCl3 3. Li 5% DTBB , THF 4. H2O Ar = 4-r-butylphenyl Guijarro, P.: Yus. M. Te.trahe.drnn. 1995, 51, 11445

REVIEW: "The Asymmetric Cyclopropanantion of Acyclic Allylic Alcohols: Efficient Stereocontrol with lodomethylzinc Reagents," Charette. A.B.: Marcoux, J.-F. Synlett, 1995, 1197 SECTION 75:

ALKYLS, METHYLENES AND ARYLS FROM MISCELLANEOUS COMPOUNDS PhMe2SiH, 1% Rh2(OAc)4

SiMe2Ph

CH 2 Cl 2 ,rt 73% Landais. Y.: Planchenault, D.; Weber, V. Tetrahedron Lett., 1994, 35, 9549

SO2r-Bu 2 PhMgBr , 5% NiCl2(PPh3)2

77%

Clayden, J.; Cooney, J.J.A.; Julia. M. J. Chem. Soc., Perkin Trans. 1., 1995, 7 REVIEW: "Organonickel Chemistry in Organic Synthesis. Some Applications of Alkyl and Metalacyclic Derivatives," C&npora, J.; Paneque, M.; Poveda, M.L.: Carmona. E. Synlett.

1994, 465

100

Compendium of Organic Synthetic Methods, Vol 9

Section 77

CHAPTER 6 PREPARATION OF AMIDES

SECTION 76: AMIDES FROM ALKYNES NH2

0.3 Rh<j(CO)i6,CO,H 2 0 dioxane, NEt3 ,175°C -Ph

Hirao, K.; Morii, N.; Job, T.; Takahashi. S. Tetrahedron Lett., 1995, 36, 6243 SECTION 77: AMIDES FROM ACID DERIVATIVES l.Sn[N(TMS) 2 ]2,THF,rt PIT

^^

"OH

2. /

j^

i4h

Bumell-Curty, C.; Roskamp. E.J. Tetrahedron Lett., 1993, 34, 5193 TiCLj, Li, Me3SiCl CsF, N2 PI Cl

Ptf

NH2

77% Kawaguchi, M.; Hamaoka, S.; Mori. M. Tetrahedron Lett., 1993, 34, 6907

Jursic. B.S.: Zdravkovski, Z. Synth. Commun., 1993, 23, 2761

H

Section 78

Amides from Alcohols

101

O

Ph

cr ^-~^»n NMM, PhCl, microwave

BnC^ ''*'

-\ Me

O'

>

75°C, 2 min

Me

/n ^

BnQ

O

(20 : Bose, A.K.; Banik, B.K.; Manhas. M.S. Tetrahedron Lett., 1995, 36, 213

PhCH-NPh , toluene ,

^

Me

80) no yield

/Ph 40% (5:95 cis:trans)

'Cl

O' 'Ph Browne, M.; Burnett, D.A.; Caplen, M.A.p; Chen, L.-Y.; Clader, J.W.; Domalski, M.; Dugar, S.; Pushpavanam, P.; Sher, R.; Vaccaro. W.: Viziano, M.; Zhao, H. Tetrahedron Lett., 1995, 36, 2555

l.NCS,PPh 3 ,CH 2 Cl 2

Bn

2.BnNH2 Frdven. P. Synth. Commun., 1995, 25, 959

PhCOOH

1. NsCl, NEt3 , DMAP/MeCN, rt 2. PhNH 2 , rt

JL

95% Lee. J.C.: Cho, Y.H.; Lee, H.K.; Cho, S.H. Synth.Commun., 1995, 25, 2877

SECTION 78: AMIDES FROM ALCOHOLS AND THIOLS ,OH

CoCl2, Ac2O , MeCN NHAc

70% Mukhopadhyay, M.; Reddy, M.M.; Maikap, G.C.; labaLJ./ Org. Chem., 1995, 60, 2670

-OH

MeCN,BF,OEt2

\ / Firouzabadi. H.: Sardarian, A.R.; Badparva, H. Synth. Commun., 1994, 24, 601

102

Compendium of Organic Synthetic Methods, Vol 9

Section 81

SECTION 79: AMIDES FROM ALDEHYDES NO ADDITIONAL EXAMPLES

SECTION 80:

AMIDES FROM ALKYLS, METHYLENES AND ARYLS PPA, AcOH, NH2OH«HC1 110°C,14h

\J~\

Cablewski, T.; Gurr, P.A.; Raner, K.D.; Strauss. C.R. J. Org. Chem., 1994, 59, 5814 SECTION 81: AMIDES FROM AMIDES Conjugate reductions of unsaturated amides are listed in Section 74D (Alkyls from Alkenes).

I

MHrvx.™ NHCC^Me

l.Mg,MeOH,0°C->rt IMIIOI

0

x'Xx'xXX*CO2Et H

91% (>99%ee)

Wei, Z.-Y.; Knaus. E.E. Tetrahedron Lett., 1993, 34, 4439 2.1TBSOTf,23°C 4.2NEt 3 ,1.75h

OMe

2.1 TBSOTf,23°C

H

4.2 collidine , 2h

49% Keck. G.E.: McHardey, S.F.; Murry, J.A. Tetrahedron Lett., 1993, 34, 6215

pw(OAc)2, KOH

r"""\ L /

\

I CH2OTBS

72%

MeOH ^=/ NHCO2Me O Moriartv. R.M.: Chany II, CJH.; Vaid, R.K.; Prakash, O.; Tuladhar, S.M. /. Org. Chem., 1993, 58, 2478

Section 81

Amides from Amides

cr "N' H

103

PhMgBr,THF

OEt

^~

- cr

N H

/ —-Ph Ph

Wei, Z.Y.; Knaus. E.R Org. Prep. Proceed. Int., 1993, 25, 255 1. 2 eq. s-BuLi, (-)-sparteine PIT

^

^NHMe

2 MeI

'

H PIT

Me ^ 'NHMe 84% (78% ee)

Beak. P.: Du, H. J. Am. Chem. Soc., 1993, 115, 2516 P II

4.2 eq. CuBr2«LiOf-Bu O -. Ph-" ^NH2 rt,6h PhHN-^^ Yamaguchi, J.; Hoshi, K.; Takeda. T. Chem. Lett., 1993, 1273

I 77% f

, acetone, 0°C

71%

N H OH Neset, S.M.; Benneche, T.; Undheim, K. Acta Chem. Scand. B., 1993, 47, 1141

NH2

CF3S03H,CH2C12 0.75 h , 20°C

_ (+ 4% lactone)

Marson. C.M.: FaUah, A. Tetrahedron Lett., 1994, 35, 293

DIAD,PPh 3 ,THF 52%

O DIAD - diisopropylazodicarboxylate Walker. M.A. Tetrahedron Lett., 1994, 35, 665

"O

104

Compendium of Organic Synthetic Methods, Vol 9

Section 81

l.Br 2 2. NEt3 2.NEI 3.BnNH2

Bn

-A/, ^ \

(S)

4. Mg(OMe)2 , MeOH

86x79%

H

O Garner. P.: Dogan, O.; Pillai, S. Tetrahedron Lett., 1994, 35, 1653

OEt

!.(PhCO) 2 O,PhH,renux 2. BuaSnH , AIBN , PhH

S

67%x"high yield" Axon, J.; Boiteau, L.; Boivin, J.; Forbes, J.E.; Zard. S.Z. Tetrahedron Lett., 1994, 35, 1719 iPrOH , 80°C, Ih

-

•*•

Ph-^~\

H

85%

OTf H Hoffman. R.V.: Nayyar, N.K.; Shankweiler, J.M.; Klinekole III, B.W. Tetrahedron Lett., 1994, 35, 3231

C 7 Hi«jCHO,H 2 ,40bar Pd/C-Na2SO4)EtOAc

o

..

*•

V

>x*^

93%

100°C H CgH17 Fache, F.; Jacquot, L.; LeMaire. M. Tetrahedron Lett., 1994, 35, 3313

C1

j-BuLi/TMEDA, THF -78°C, 5h

Beak. P.: Wu, S.; Yum, E.K.; Jun, Y.M. J. Org. Chem., 1994, 59, 276

? Boc

82%

Section 81

Amides from Amides

ft

105

PhCHO , PPE , 60°C , 16h NH2

PPE = polyphosphoric ester Marson. C.M.: Grabowska, U.; Eallah, A.; Walsgrove, T.; Eggleston, D.S.; Baures, P.W. J. Org. Chem., 1994, 59, 291

.1.3 eq. POC13, -78°C 2. 3.5 eq. TMS2S , -78°C -» rt, 4h

Smith, D.C.; Lee, S.W.; Fuchs. P.L. J. Org. Chem., 1994, 59, 348 BnNH2 , A1C13 , 90°C 'NH 2

^

NHBn 67%

Bon, E.; Bigg. D.C.H.: Bertrand. G. J. Org. Chem., 1994, 59, 4035

1.2j-BuLi/2TMEDA THF , -78°C , 8h

N

-Or-Bu

2fiul

N

0,-Bu

CH3 CH2Bu ?0% Snieckus. V.: Rogers-Evans, M.; Beak. P.: Lee, W.K.; Yum, E.K.; Freskos, J. Tetrahedron Lett., 1994, 35, 4067 BusSnH , cat. AIBN (addn over 4 h) degassed cyclohexane

O

0 66% Me O Callier, A.-C.; Quiclet-Sire, B.; Zard. S.Z. Tetrahedron Lett., 1994, 35, 6109

106

Compendium of Organic Synthetic Methods, Vol 9

Section 81

BuaSnH, AIBN 'N

PhH (0.5M)

\

/

87%

Keusenkothen, P.F.; Smith. M.B.7. Chem. Soc., Perkin Trans. L, 1994, 2485 NHTs

f

A.

iPrMgCl, THF, 0°C , 6h

'Ph

(45 : 57) 63% Toshimitsu. A.: Abe, H.; Hirosawa, C.; Tamao, K. J. Chem. Soc., Perkin Trans. L, 1994, 3465

65% x low yield Ciganek. E.: Wuonola,M.A.; Harlow, R.L. J. Heterocyclic Chem., 1994, 31, 1251 l.BtCH2OH 2. CH2=CHCH2SiMc3 63% BF3-OEt2 O Katritzkv. A.R.: Ignatchenko. A.V.: Lang. H. J. Org. Chem., 1995, 60, 4002 OMe

Bu3SnH , AIBN , PhH reflux , 8h (syringe pump , 7h)

30%

; Whang, U.S.; Chung, C.K. Tetrahedron Lett., 1995, 36, 913

,,a 36%

Section 81

Amides from Amides

9

107

(BnNEt3)2MoS4, CH£12

j?

Ph

"~"^ NMe2 -78°C -» rt, 30 min Ph^"\ Ilankumaran, P.; Ramesha, A.R.; Chandrasekaran. S. Tetrahedron Lett., 1995, 36, 8311 1. 2.2 eq. BuLi, THF, -78°C -» 0°C 2. 9 PIT

_.Ph

NHMe

3. 4. Me3SiCl, Nal, MeCN

Kiselvov. A.S Tetrahedron Lett., 1995, 36, 493

p.

^ ^- N^ I J- S02 PIT

Ph

2SnCl2,2KI CH 2 Cl 2 ,rt,12h

53% + 10% benzophenone Kataoka. T.: Iwama, T. Tetrahedron Lett., 1995, 36, 5559

O HCsCCH2Br, PME/DMF, NaH LiBr, 0°C -» rt

TH Liu, H.; Ko, S.-B.; Josien, H.; Curran. P.P. Tetrahedron Lett., 1995, 36, 8917

Ph Mn(OAc)3

"X

AcOH

S ^ Ph

39% O

P'Annibale, A.; Resta, S.; Trogolo, C. Tetrahedron Lett., 1995, 36, 9039

108

Compendium of Organic Synthetic Methods, Vol 9

Section 82

2% Rh2<SSMEPY)4

V

O

CH2Cl2

"

CHN2 Dovle. M.P.: Kalinin, A.V. Synlett, 1995, 1075

O

70% (96% ee)

Ph MeS 66% •Ar

Ishibashi. H.: Nakaharu, T.; Nishimura, M.; Nishikawa, A.; Kameoka, C.; Ikeda, M. Tetrahedron, 1995, 51, 2929 Ph

toluenhe , reflux

+x

^ff ^ff

I

Me

Me

J

47% 12% Sato, T.; Chono, N.; Ishibashi, H.: Ikeda. M. J. Chem. Soc., Perkin Trans. L, 1995, 1115

©0 Me2S—CHCO2Et

41% N-

Tol02S/ Nadir. U.K.: Arora, A. / Chem. Soc., Perkin Trans. L, 1995, 2605

SECTION 82: AMIDES FROM AMINES NaBO3-4 H f > , CF3CO2H =N-Ph

80°C

H

Nongkunsarn, P.; Ramsden. C.A. Tetrahedron Lett., 1993, 34, 6773

*V Ph

51%

Section 82

Amides from Amines

NHBn

109

Sn[N(TMS)2]2, hexane, rt CO2Me

C3H-T

pivalicacid

Bn

C3Hf Wang, W.-B.; Roskamp. E.J. 7. Am. Chem. Soc., 1993, 115, 9417 NCCH2CHO, rt, 6h CgHn—NH2 — +- CgHn—NHCHO Duetsch, J.; Niclas. H.-J. Synth. Commun., 1993, 23, 1561 / \

x

\

1. N-cyclohexyl-N1,N',N",N"tetramethylguanidine, pyridine

/ '

toluene, CO2,-10°C 2. toluene, SOC12 , -10°C

/ \ >

v

P

/* '

\

C1

77%

McGhee. W.D.: Pan, Y.; Talley, J.J. Tetrahedron Lett., 1994, 35, 835

?

H2N

/ 1* I

V

^ OH

3eq.NEt 3 ,THF 2. excess NaH

W / \

67%

Osborn, H.M.I.; Cantrill, A.A.; Sweeney. J.B.: Howson, W. Tetrahedron Lett., 1994, 35, 3159

xylene , 150°C , 3h -- OEt

NHBn MaGee. PI: Ramaseshan, M. Synlett, 1994, 743 CO,MeCN,65°C OTf

Crisp. G.T.: Meyer, A.G. Tetrahedron, 1995, 51, 5585

O

quant.

110

Compendium of Organic Synthetic Methods, Vol 9

. dPPP

'NEt2

Section 83

* O

78%

Murahashi. S.-I.: Imada, Y.; Nishimura, K. Tetrahedron, 1994, 50, 453

SECTION 83: AMIDES FROM ESTERS H—

,OAc K2CO3 , rt, Id 77% Genet. J-P.: Thonmbert, S.; Touzin, A-M. Tetrahedron Lett., 1993, 34, 1159

2eq. Sn[NTMS2l2 2 eq. Me2NCH2CMe2OH 2 eq. PhCHMeNH2

^

H Wang, W.-B.; Restituyo, J.A.; Roskamp. E.J. Tetrahedron Lett., 1993, 34, 7217

97%

1.5Sn[N(TMS)2]2,THF Ph

OMe

1 -5 Et2NH-HCl, rt, 18h

52% Smith, L.A.; Wang, W.-B.; Burnell-Curty, C.; Roskamp. E.J. Svnlett. 1993, 850 O

iPrNH 2 ,f-BuOH,1.5d 25°C

j H

69%

Chen. S.-T.: Chen, S.-Y.; Chen, S.-J. Tetrahedron Lett., 1994, 35, 3583 NaEt2Al(Bn)2, toluene reflux , Ih

C3H7

^ ^NHBn 93%

Sim, T.B.; Yoon. N.M. Svnlett. 1994, 827

Section 85

Amides from Halides

O

ph

M

f -l

2. NEt3, CH2C12

111

p

M

Ov

'PMP (f 'PMP PMP = 4-methoxyphenyl /^Q . ^Q\ 99% Annunziata. R.: Benaglia, M.; Cinquini, M.; Cozzi, F.; Ponzini, F.; Raimondi, L. Tetrahedron, 1994, 50, 2939 OH

1. BCl3-SMe2

Ph

A Me Y NMe2

SPy

2.

74% (78% ee)

Ph~^\ N N—PMP

^—< CT ^PMP PMP = N-4-methoxyphenyl Annunziata, R.; Benaglia, M.; Cinquini. M.: Cozzi. F. Tetrahedron Lett., 1995, 36, 613

SECTION 84:

AMIDES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDITIONAL EXAMPLES

SECTION 85: AMIDES FROM HALIDES AND SULFONATES

l.Mg

2. PhNCO SiMe3 Cooke Jr.. M.P.: Pollock, C.M. J. Org. Chem., 1993, 58, 7474

,MgBr

cat. NiQ2(dppe) , THF , rt 90%

Babudri, F.; Fiandanese, V.; Marchese. G.: Punzi, A. Synlett, 1994, 719

112

Compendium of Organic Synthetic Methods, Vol 9

Section 87

1. CS2 , THF 2. BtSO2CF3 \\ PhMgBr -—-^II 3.BuNH2 T^ Bt = benzotriazol-l'-yl Katritzkv. A.R.: Moutou, J.-L.; Yang, Z. Synlett, 1995, 99

„_ II

SECTION 86: AMIDES FROM HYDRIDES NO ADDITIONAL EXAMPLES SECTION 87: AMIDES FROM KETONES

00

aldehydes can also be used

Me02C

^^

NH2

TEA, NaBH(OAc)3 DCE , rt, 45h

Abdel-Magid. A.F.: Harris, B.D.; Maryanoff, C.A. Synlett, 1994, 81 OTIPS

1. 10eq.TMSN3 2 eq. PPTS CH2C12, rt, 2d 2. UV, 0°C, Ih 79x89%

Evans. P.A.: Modi, D.P. 7. Org. Chem., 1995, 60, 6662

N3

0.75 h

/

83%

Milligan, G.L.; Mossman, C.J.; Aub6, J. 7. Am. Chem. Soc., 1995, 117, 10449

o . NH2OSO3H , SiO2 2. H 2 O, microwave

/N

H

Laurent, A.; Jacquault, P.; Di Martino, J.-L.; Hamelin. J. 7. Chem. Soc. Chem. Commun. 1995, 1101

Section 89

Amides from Alkenes

113

SECTION 88: AMIDES FROM NITRILES UHP, cat. K2C03 . aq. acetone PhCN

rt, In

NH2

UHP = urea-hydrogen peroxide adduct Balicki. R.: Kaczmarek, L. Synth. Commun., 1993, 23, 3149 MnO2, SiO2, hexane

Breuilles, P.; Leclerc, R.; Uguen. D. Tetrahedron Lett., 1994, 35, 1401

CN

A12O3 (neutral), 60°C , Id

\

P

- yj^

7Q^

/ ^NH 2 Wilgus, C.P.; Downing, S.; Militor, E.; Bains, S.; Pagni. R.M.: Kabalka. G.W. Tetrahedron Lett., 1995, 36, 3469 SECTION 89: AMIDES FROM ALKENES i. / u

TsN=IPh, Mn salen catalyst

A p, 34% Ph rPhn 1Z_N_ N pyridine N-oxide, MeCN , rt ^ Ts Noda, K.; Hosoya, N.; Irie, R.; Ito, Y.; Katsuki. T. Synlett, 1993, 469 1. PhI=NTs , Cu(OTf)2, MeCN '

^

js,

2.0.1MNaOH 77%

Knight. J.G.: Muldowney, M.P. Synlett, 1995, 949 SECTION 90:

AMIDES FROM MISCELLANEOUS COMPOUNDS BnN=C=O, hv (Pyrex filter) 42%

Cr(CO)3 Rigbv. J.H.: Ahmed, G.; Ferguson, M.D. Tetrahedron Lett., 1993, 34, 5397

114

Compendium of Organic Synthetic Methods, Vol 9

( >=N-OH \_ /

Section 90

50% H2NOH«HC1

Narasaka, K.; Kusama, H.; Yamashita, Y.; Sato, H. Chem. Lett., 1993, 489

2.5TMSOTf,CH£l2

Ph

30% (>95:5 endo:exo) Pouilhds, A.; Langlois. Y.: Nshimyumu Kiza, P.; Mbiya, K.; Ghosez. L. Bull. Soc. Chim. Fr., 1993, 130, 304 l.MeMgCl 2.BEt 3 _ -^ ^ Pb^\ Me 3.H2NOS03H Huang. H.-C.: Reinhard, E.J.; Reitz, D.B. Tetrahedron Lett., 1994, 35, 7201

50%

hv, hexane, PhNMe2

* W~

no yield

Post, AJ.; Nwaukwa, S.; Morrison. H. 7. Am. Chem. Soc., 1994, 116, 6439 N02

CO,MeOH,7b Pd(dppp)Cl2,PhH

^

^NHCOzMe

K2CO3, MeO2CHN 02N Reddy, N.P.; Masdeu, A.M.; El Ali, B.: Alper. H. 7. Chem. Soc. Chem. Commun., 1994, 863

Section 90A

Protection of Amides

Mn(tpp)Cl, MeCN

115

Ph

~

30°C

v^

tpp = tetraphenylporphyrin ° 60% Suda. K.: Sashima, M.; Izutsu, M.; Hino, F. J. Chem. Soc. Chem, Commun., 1994, 949

Ph

\ >=N—OH / Me

Montmorillonite K-10, microwave *7min

Me. \

Jt // O

,.„,„. NHph 91%

(17% with heating and no microwave) Bosch, A.I.; de la Cruz, P.; Diez-Barra, E.; Loupy, A.: Langa. F. Svnlett. 1995, 1259

DMF, POC13 ,90°C,. 5h

N-OH Majo, V.J.; Venugopal, M.; Prince, A.A.M.; Perumal. P.T. Synth. Commun., 1995, 25, 3863

N-OH 0.2 Bu4NReO4,0. MeNO2, reflux, 0.5 NH2OH'HC1

Ph'

Ph Kusama, H.; Yamashita, Y.; Narasaka, K. Bull. Chem. Soc. Jpn., 1995, 68, 373 SECTION 90A:

PROTECTION OF AMIDES O

2 Mn(OAc)3-2 H2O, EtOH Cu(OAc)2»H20,55°C

Ghosh, A.; Miller. M.J. Tetrahedron Lett., 1993, 34, 83

91%

116

Compendium of Organic Synthetic Methods, Vol 9

Section 90A

1. A1C13,60°C 2. PhOMe, 6h

-OH

60%

Pti"

^Ci

H (9:1 p:o)

~J

\^

Kim, J.N.; Rvu. E.K. Tetrahedron Lett., 1993, 34, 3567

Mg(C104)2,MeCN

.uoc

^

V 50°C,20h ™^\, 99% Me Stafford. J.A.: Brackeen, M.F.; Karanewsky, D.S.; Valvano, N.L. Tetrahedron Lett., 1993, 34, 7873

Mg(OMe>2, MeOH

o Wei, Z.-Y.; Knaus. E.E. Tetrahedron Lett., 1994, 35, 545 5 eq. Ac 2 0, 4% Pd(PPh3)4 2.2 eq. Bu3SnH , CH2C12

58% Roos, E.C.; Bernabd, P.; Hiemstra. H.: Speckamp. W.N.: Kaptein, B.; Boesten, W.H.J. J. Org. Chem., 1995, 60, 1733

Section 93

Amines from Alcohols

117

CHAPTER 7 PREPARATION OF AMINES

SECTION 91: AMINES FROM ALKYNES NO ADDITIONAL EXAMPLES SECTION 92: AMINES FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES SECTION 93: AMINES FROM ALCOHOLS AND THIOLS l.MeLi,THF

f

•"^f

""^i"" 47%

2. PhCN,warm 'OH Fitzgerald, J.J.; Michael, F.E.; Olofson. R.A. Tetrahedron Lett., 1994, 35, 9191 •OH

1. BuN3 , 2.5 eq. TfOH

'Me

2.NaBH4

95% Bu

Pearson. W.H.: Fang, W. J. Org. Chem, 1995, 60, 4960 PhCH2OH

PhCH2NHTf , DEAD , PPh3 -^

(PhCH2)2N—Ts

93%

Bell, K.E.; Knight. D.W.: Gravestock, M.B. Tetrahedron Lett., 1995, 36, 8681 HNBn2, SnCl2 , NEt3 , THF , 2d OH

2% Pd(PPh3)4,50°C

>

NBn2 70%

Masuvama. Y.: Kagawa, M.; Kurusu, Y. Chem. Lett., 1995, 1121

118

Compendium of Organic Synthetic Methods, Vol 9

Section 94

SECTION 94: AMINES FROM ALDEHYDES

PhCHO

«~

Me3SiCl, 29h

> '

N *

©

I '

92%

Cl

Jahn, U.; Schroth. W. Tetrahedron Lett., 1993, 34, 5863 / ( \

\ ) f

1. CsH i iCHO , BER, EtOH NH2

*-

(

)

Et3NHCl 2. BER, NaOH

NHCH2C5HU

BER = borohydride exchange resin Yoon. N.M.: Kim, E.G.; Son, H.S.; Choi, J. Synth. Commun., 1993, 23, 1595 HO

LiAl(NHBn)4, ether

\

89%

/=N-Bn

25°C, 7h Solladi6-Cavallo. A.: Bencheqroun, M.; Bonne, F. Synth. Commun., 1993, 23, 1683

> 1

Bzt-SNH2 , NaOH , EtOH PhSN(TMS)2, cat. TB AF, THF

Ph

\ C >

i

>

3. 3. BusSnH, cat. AIBN, cyclohexane CHO

N

61x69%

Boivin, J.; Fouquet, E.; Zard. S.Z. Tetrahedron, 1994, 50, 1745 Ph^-v. pn

^CHO

1. Me2NH«HCl, Ti(OiPr)4, NEt3 EtOH , 25°C , lOh 2.NaBH4,25°C , lOh

"

Bhattacharvva. S. J. Org. Chem., 1995, 60, 4928 1. BnNH2, Py»BH3 , MeOH MS 4A, 16h

^^^ ^^ P I T ^ N^^ Ph PhCHO ^ I 2.6NHC1 H 3. 8 N NaOH 87% Bomann, M.D.; Guch, I.C.: DiMare. M. J. Org. Chem., 1995, 60, 5995 TsNH2 , Si(OEt)4 ,160°C , 6h PhCHO *PhCH=NTs Love. B.E.: Raje, P.S.; Williams II, T.C. Synlett, 1994, 493

Section 96

Amines from Amides

119

, Bentonite, rt, 3h *• PhCH=N-Bn ketones can also be used Saoudi, A.; Benguedach, A.; Benhaoua. H. Synth. Commun., 1995, 25, 2349 PhCHO

Related Methods: Section 102 (Amines from Ketones)

SECTION 95:

AMINES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES

SECTION 96: AMINES FROM AMIDES O

LiBH3BN(iPr)2

c

6Hi3

THF,rt 95%

Fisher, G.B.; Fuller, J.C.; Harrison, J.; Goralski, C.T.; Singaram. B. Tetrahedron Lett., 1993, 34, 1091 KH , THF, Cp2ZrHCl

^C joH21

'h—" Ph—^KJHC nH "* rt Schedler, D.J.A.; Godfrey, A.G.; Ganem. B. Tetrahedron Lett., 1993, 34, 5035 1. LiHMDS; BnBr 2.LiHMDS;MeI 3. LiAlH4 4. H 2 , Pd-C

Tr ^

^^ Me

Ph' Westrum, L.J.; Mevers. A.I. Tetrahedron Lett., 1994, 35, 973

TiCl3 , 3 eq. C8K

Furstner. A.: Hupperts, A.; Ptock, A.; Janssen, E. J. Org. Chem., 1995, 60, 5215

120

Compendium of Organic Synthetic Methods, Vol 9

HBr, 163°C /

S\_ //N

*-

Section 97

/ H—N

\ N—Ph

NHPh-HBr

88% Poindexter. G.S.: Bruce, M.A.; LeBoulluec, K.L.; Monkovic, I. Tetrahedron Lett., 1994, 35, 7331 .

h

N

/ -N

f-Bu 52% Bozee-Ogor, S.; Salou-Guiziou, V.; Yaouanc, J.J.; Handel. H. Tetrahedron Lett., 1995, 36, 6063

Ph 3 Ti (powder) , THF , 21h 3 TMSC1 , reflux

99% Fiirstner. A.: Hupperts, A. 7. Am. Chem. Soc., 1995, 117, 4468

H

C

N

30% H2O2 , AcOH , 25°C

\\

N \

\

Me

Me Grivas, S.; Ronne, E. Acta Chem. Scand. B., 1995, 49, 225

Related Methods: Section 105 A (Protection of Amines) SECTION 97: AMINES FROM AMINES

N—Ph

^

1.5 Li (powder), THF cat. Ci0H8 , -78°C, 6h

2. H20 Almena, J.; Foubelo, F.; Yus. M. Tetrahedron Lett., 1993, 34, 1649

H

Section 97

Amines from Amines

Me

_ H

121

PhCHO , TFA Et3SiH , CH2C12 , 0°C

H Appleton, J.E.; Back, K.N.; Green, A.B.; Steele. J. Tetrahedron Lett., 1993, 34, 1529

^ -

9-BBN , THF, 20h

£U H Ar = 3,4-dimethoxyphenyl Gaul, M.D.; Fowler, K.W.; Grieco. P.A. Tetrahedron Lett., 1993, 34, 3099

Bn

_

Bn

:' V^/^|

~2^0*

] ~T

\

70%

Maye, J.P.; Negishi. E. Tetrahedron Lett., 1993, 34, 3359

'h

Ph

10eq.MeLi,PhH,50°C

NH2 20%

X50% Genin, M.J.; Biles, C.; Romero. B.L. Tetrahedron Lett., 1993, 34, 4301

/ \

\ /

1.5-BuLi,TMEDA 2. Mel

^N 3.5-BuLi, TMEDA | 4. Mel Boc ; Lee, W.K. J. Org. Chetn., 1993, 58, 1109

/ \

\ /

/^ N^^Me | Boc

Me

62x41%

122

Compendium of Organic Synthetic Methods, Vol 9

Section 97

f-Bu 1.1.5LDA,THF,0°C

—s \^

2. 1.2

f

%

62%

Me2 THF , 15h , 0°C -> rt

3. 3 eq. K2CO3 , MeOH heat , 3h E)eKimpe. N G : Keppens, M.A.; Stevens, C.V. Tetrahedron Lett., 1993, 34, 4693

2.5 eq. LiBHEt3 , THF, rt ""

-X*^

^v.

(1:1 cis:trans) H

Blough, B.E.; Carroll. F.I. Tetrahedron Lett., 1993, 34, 7239

O

1. Li, THF 2. PhBr, THF, rt, 6h

3. MeOH ; 20% HC1 H Kanth, J.V.B.; Periasamv. M. J. Org. Chem., 1993, 58, 3156

Ph

5% Pd(OAc)2, 5% PPh3 100°C,3.5d,Na2C03 X^X^ 65% Larock. R.C.: Berrios-Pefia, N.G.; Fried, C.A.; Yum, E.K.; Tu, C.; Leong.W. J. Org. Chem., 1993, 58, 4509 CO2Me ONMe2 , Me3COCl

Me

2. Tol, 120°C , 20h

' \ 65 x 60% H Soderberg, B.C.; Helton, E.S.; Austin, L.R.; Odens, H.H. J. Org. Chem., 1993, 58, 5589 'NH2

Section 97

Amines from Amines

, cat. Tl complex U. 65°C, 7h

123

^o

__ _ ph^^M^ | H Willoughby, C.A.; Buchwald. S.L. J. Org. Chem., 1993, 58, 7627

(99% ee)

acetone, NaBH4, 3M H2SO4, THF PhNH2 *~ PhNHiPr Verardo, G.; Giumanini. A.G.: Strazzolini, P.; Poiana, M. Synthesis, 1993, 121

/ \ \ ^ ^ OEt I

®

95%

1. styrene , MeNO2 , reflux 2.NaBH 4 ,EtOH

Sheu, J.; Smith. M.B.: Matsumoto, K. Synth. Commun., 1993, 23, 253

6 SmI2 , 28 H2O , THF rt, 90 min

rw

" Kamochi. Y.: Kudo, T. Heterocycles, 1993, 36, 2383

95% A i

H

BU3SnH, cat. AIBN cyclohexane Ph

additon over 4 h O Boivin, J.; Schiano, A.-M.; Zard. S.Z. Tetrahedron Lett., 1994, 35, 249

Na2S2O4-K2C03-H2O toluene, 100°C , 15h

the reaction fails for many N-R where R * Bn Wong, Y.-S.; Marazano. C.: Gnecco, D.; Das, B.C. Tetrahedron Lett., 1994, 35, 707

124

Compendium of Organic Synthetic Methods, Vol 9

Section 97

1 • Br 2 , CH2C12 ,0°C 2. 2 eq. LiAlH4, ether

DeKimpe, N.; Boelens, M.; Piqueur, J.; Baele, J. Tetrahedron Lett., 1994, 35, 1925

f~\ ( N \

(HCHO)n,Ti(OiPr)4 — 2.NaBH4

H

/

/ < \

\ N—Me /

95%

Bhattacharyya. S. Tetrahedron Lett., 1994, 35, 2401 Ph

v \T „ N—H /

l.MeMgCl,THF,rt 2. Cp^rCh, THF 3. hexane/dioxane, rt

*4. MeMgCl, -30°C -^ rt

¥ J.

„. Ph>

5 MeOH

' Ph Harris, M.C.J.; Whithv. R.J.: Blagg, J. Tetrahedron Lett., 1994, 35, 2431 *SnBu3

78%

,y.

Me (10 Pearson. W.H.: Stevens, E.P. Tetrahedron Lett., 1994, 35, 2641

:

1) 88%

1.2f-BuLi 2. inline 3. TFA, CH2C12

65% Reuter. D.C.: Flippin. L.A.: Mclntosh, J.; Caroon, J.M.; Hammaker, J. Tetrahedron Lett., 1994, 35, 4899

Y Pn

ph

*RHN

NHR* *RHN

NHR*

(6 1) 47% Bambridge, K.; Begley, M.J.; Simpkins. N.S. Tetrahedron Lett., 1994, 35, 3391

Section 97

Amines from Amines

125

'Ac

MeCN,NaPF6 2% Pd(Ph3)4 NMe2 Grellier, M.; Pfeffer. M.: van Koten, G. Tetrahedron Lett., 1994, 35, 2877 N-f-Bu

-t-Eu 3 eq. LDA , THF, rt, 16h 55%

Stevens, C.V.; De Kimpe. N.G.: Katritzky, A.R. Tetrahedron Lett., 1994, 35, 3763

JL LiEt2NBH3, THF, 0°C JL N Ph ^ HN Ph lh II L.H 95% \ Fuller, J.C.; Belisle, C.M.; Goralski, C.T.; Singaram. B. Tetrahedron Lett., 1994, 35, 5389 PhS< Bu3SnH , AIBN , PhMe addn via syringe pump P 56% " " Bowman. W.R.: Stephenson, P.T.; Terrett, N.K.; Young, A.R. Tetrahedron Lett., 1994, 35, 6369

0.05 Pi4N RuO4 ,1.5 NMO MeCN, rt, Id ,NH

Goti. A.: Romani, M. Tetrahedron Lett., 1994, 35, 6567 Br

.s^

J

r ^-^

NaBH 4 ,MeOH,heat

/

/

^ \ xN/

Pt De Kimpe. N.: De Smaele, D. Tetrahedron Lett., 1994, 35, 8023

\

Ph

126

Compendium of Organic Synthetic Methods, Vol 9

Section 97

\ X 5% chiral Ti catalyst , H2 , THF , rt C / N -^ N I 75% (92% ee, R)

^ S.L. 3. Am. Chem. Soc., 1994, 116, 5985 Lee, N.E.; Buchwald. Etv ,Et Et O^.XS.^0

i rj>\

,OMe

T

M^HC

F

'CHM&2

2 MeLi, toluene, -78°C

H£T I 5^

90% (70% ee, R) Me Denmark. S.E.: Nakajima, N.; Nicaise, O.J.-C. 7. Am. Chem. Soc., 1994, 116, 8797

. Cp2ZrBu2, THF, -78°C Bn — N

2. aq. MeOH 70%

Kemp, ML; Whitbv. R.J.: Coote, SJ. Synlett, 1994, 451 NH Ph-^CPhpH (10%)

BH3-SMe2 2. workup 68% (50% ee , S)

Bolm. C.: Felder, M. Synlett, 1994, 655

PhS

49% (2.8 : 1.2:1 (minor product) Bowman. W.R.: Clark, D.N.; Marmon, RJ. Tetrahedron, 1994, 50, 1295

Section 97

Amines from Amines

/ \ ( N— Bn \_ /

127

l.DCE,ClCO2Et / -*2.

\ N— H 80%

Kanth, J.V.B.; Reddy, Ch.K.: Periasamv. M. Svnth. Commun., 1994, 24, 313 l.(HCHO) n ,ZnCl 2 ,THF 2.Zn(BH 4 ) 2 ,THF,25°C,lh 3. aq. NH3 70%

Bhattacharyya. S.: Chatterjee, A.; Duttachowdhury, S.K. J. Chem. Soc., Perkin Trans. 1., 1994, 1

l.NCS,PhH V

NHMe

Me 2. BugSnH , AIBN, PhH , reflux

| M Me

Me 42%

Tokuda. M.: Fujita, H.; Suginome. H. /. Chem. Soc., Perkin Trans. 1., 1994, 111 /= ,48%HBr

^/^^NHf-Bu

dioxane, sealed tube 100°C, 4d Gage. J.R.: Wagner, J.M. J. Org. Chem., 1995, 60, 2613 Me(Q >= , 100°C,9h

.

PPTs , NEt3 , sealed tube

PPTs = pyridinium p-toluenesulfonate Morris. J.: Wishka, D.G. J. Org. Chem., 1995, 60, 2642

_ NaCNBH4,MeOH

\ / \ 75% N / Me Gillaspv. M.L.i Lefker. B.A.: Hada, W.A.; Hoover, D.J. Tetrahedron Lett., 1995, 36, 7399

128

Compendium of Organic Synthetic Methods, Vol 9

Section 97

0.2 MeLi, SnMe4, THF

Coldham. I.: Hufton, R. Tetrahedron Lett., 1995, 36, 2157 /

\

1. s e c -BuLi, TMEDA 2. Phi, [P(o-Tol)3]4Pd-CuCN 75°C , 18h , toluene

^

V Boc Dieter. R.K.: Li, S. Tetrahedron Lett., 1995, 36, 3613

54%

^X^ Ph

V Boc

B

\

•CO2Me

In,THF,15h 50% "C02Me Bossard, F.; Dambrin, V.; Lintanf, V.; Beuchet, P.; Mosset. P. Tetrahedron Lett., 1995, 36, 6055 Me

§u

MeO

BuLi, ether, 0°C LiBr, 5h

Me

OMe

*• Ph" H

80% (98:2 anti:syn) Hashimoto. Y.: Kobayashi, N.; Kai, A.; Saigo. K. Synlett. 1995, 961

, AIBN, PhH , 80°C Ar = 4-chlorophenyl

^_

fl

71%

Gioanola, M.; Leardini. R.: Nanni, D.; Pareschi, P.; Zanardi, G. Tetrahedron, 1995, 51, 2039

Section 99

Amines from Ethers

129

1. (HCHO)n , ZnCl2 —-—---*2. ZnCl2 , NaBH4 , CH£12 , rt Bhattacharvva. S. Svnth. Commun., 1995, 25, 2061 Bn2NH

Bn2NMe

90%

,Ph

,HCHO

90%

MeCN, TFA, reflux O2N

s^^^

•>*'"

Mellor. J.M.: Merriman, G.D. Tetrahedron, 1995, 51, 6115 Ph

/

Ph

Pn

1. K2CO3 , KOH , BnBr, CH2C12

" •Ph

chiral ammonium ligand

2.H3O+ 2 Eddine. J.J.: Cherqaoui, M. Tetrahedron Asymmetry, 1995, 6, 1225

70%(91%ee)

Pd(dba)2, dppb

^^ ^ "

20°C , 25h quant. Me Lemaire-Audoire, S.; Savignac, M.; Dupuis, C.; Genet, J.-P. Bull Soc. Chim. Fr., 1995, 132, 1157

SECTION 98: AMINES FROM ESTERS NHEt2 , Ni(dppe)2 , THF no yield 80°C Bricout, H.; Carpentier, J.-F.; Mortreux. A. J. Chem. Soc. Chem. Commun., 1995, 1863

SECTION 99:

AMINES FROM ETHERS, EPOXIDES AND THIOETHERS

OMe

||

M—H / BuLi

_„ OMe

THF, reflux, overnight

I

I

I

^v

N^\ x -

70%

L7

ten Hoeve, W.; Kruse, C.G.; Luteyn, J.M.; Thiecke, J.R.G.; ten Hoeve, W.; Kruse, C.G.; Luteyn, J.M.; Thiecke, J.R.G.; Wynberg, H. J. Org. Chem., 1993, 58, 5101

130

Compendium of Organic Synthetic Methods, Vol 9

Section 100

SECTION 100: AMINES FROM HALIDES AND SULFONATES Br.

JSTHNPh2

SmI 2 ,THF,HMPA -42°C

\X ^N 7

< H Sturino, C.F.; Fallis. A.G. J. Am. Chem. Soc., 1994, 116, 7447

1 j BU3Sn—NEt2 , MeNHBn 1

JSTHNPh2

\ 1) 88%

:

NMeBn

5% PdCl2(Po-Tol3)2 toluene, 105°C, 4h 2.HC1 'Me 3.MeOH Guram, A.S.; Buchwald. S.L. J. Am. Chem. Soc., 1994, 116, 7901 Ph

iAmONO , Bu^>n 2 , hv (UV lamp)

Br 4h N—OH Fletcher, R.J.; Kiril, M.; Murphy. J.A. Tetrahedron Lett., 1995, 36, 323

Br

P((o-Tol)3 , LiNTMS2, 2h

*• Bu

^\

/;

N(TMS)2

piperidine, 100°C Louie, J.; Hartwig. J.F. Tetrahedron Lett., 1995, 36, 3689 BuNH2 , DMSO , 80°C j 2h OMs NHBu lin. F.: Mahuet, E.; Muller, C.; Muzart, J. Synth. Commun., 1995, 25, 1331

46%

NHMePh, Pd(dba)2/2 P(o-Tol)3 Ph

(\

/)

NMePh

65°C , toluene 88% Guram, A.S.; Rennels, R.A.; Buchwald. S.L. Anqew. Chem. Int. Ed. Engl, 1995, 34, 1348

Section 102

Amines from Ketones

131

SECTION 101: AMINES FROM HYDRIDES )Me

1. 65°C, 24h 2.Zn,AcOH "2lN 99x71% Zaltsgendler, L; Leblanc. Y.: Bernstein, M.A. Tetrahedron Lett., 1993, 34, 2441

SECTION 102: AMINES FROM KETONES

O

Westerwelle, U.; Risch. N. Tetrahedron Lett., 1993, 34, 1775 1. LDA , nitroethylene , ZnCl2, THF, -30°C 2. Ni(R), EtOH , H2 (50 psi)

X '

l

3. NaBHgCN , AcOH , EtOH , 0°C 77x95x100% Pal. K.: Behnke, M.L.; Tong, L. Tetrahedron Lett., 1993, 34, 6205

H+ , Si(OEt)4 , H2NCHPh2

O Love. B.E.: Ren, J. J. Org. Chem., 1993, 58, 5556 1,10-phenanthroline, CO », p-dioxane

91% *0

N02

140°C,16h

Watanabe. Y.: Yamamoto, J.; Akazome, M.; Kondo, T.; Mitsudo. T. / Org. Chem., 1995, 60, 8328

132

Compendium of Organic Synthetic Methods, Vol 9

Section 104

Related Methods: Section 94 (Amines from Aldehydes) SECTION 103: AMINES FROM NITRILES

0

0

PhMgCl, CH2C12 5h, -78°C -» rt

Kim, J.N.; Kim, H.R.; Ryu. E.K. Tetrahedron Lett., 1993, 34, 5117

r(CO)5

,_BuCN >r.BuOMe 0°C (Ih), reflux (2d)

OMe

-

W

^3^

JC

71%

Merlic. C.A.: Bums, E.E. Tetrahedron Lett., 1993, 34, 5401 BuMgCl, PhH/ether, rt

N Fry. P.P.: Fowler, C.B.: Pieter. R.K. Synlett. 1994, 836

Ph—CN

2 eq. HC^CH, hv, H^, 3h — r /^-/~5_csHs)(cod) 1

^w

N

Heller. B.: Oehme, G. J. Chem. Soc. Chem. Commun., 1995, 179

SECTION 104: AMINES FROM ALKENES PhNH2, PhNHLi, 12d [RhCl(PEt3)2]2,700C 65% (+ 30%N-phenyl phenethylamine and 5% N-phenyl-2-phenylethane) Brunet. J.-J.: Neibecker, D.; Philippot, K. Tetrahedron Lett., 1993, 34, 3877

Section 105

Amines from Misc.

NsONHCO2Et, CH2C12

133

- A /V

62%

Fioravanti, S.; Loreto, M.A.; Pellacani, L.; Tardella, P.A. Tetrahedron Lett., 1993, 34, 4353 1.O3,CH2C12,-78°C 2.2eq./

\_H

4A MS , CH£12 , Hon. Y.-S.: Lu, L. Tetrahedron Lett., 1993, 34, 5309

reflux

85%

,NHPh PhNHOH, Fe(Pc)

f

76% 22% PhNH2

PC = phthalocyanine Ph Johannsen, M.: Jdrgensen. K.A. J. Org. Chem., 1994, 59, 214 HZr(Cl)Cp2:RONH2

Bu,

THF 77%

R = MeAftzOSOr Zheng, B.i Srebnik. M. .7. Org. Chem., 1995, 60, 1912

SECTION 105:

AMINES FROM MISCELLANEOUS COMPOUNDS

1. BuLi, BF3«OEt2, toluene 2,LiAlH4 Bu' 70% (60% de)

Dieter. R.K.: Datar, R. Can. J. Chem., 1993, 71, 814 (EtO)3SiH, Ti(OiPr)4 * Ph^Ph PIT | ^Ph Ph 67oC Ph Coumbe, T.; Lawrence. N.J.: Muhammad, F. Tetrahedron Lett., 1994, 35, 625

134

Compendium of Organic Synthetic Methods, Vol 9

CO2Me

Section 105

LBu3SnH,AffiN MeCN, 100°C 2. PhBr, NEt3 , 100°C 5%Pd(PPh3)4

^X^^ N \ H Fukuvama. T.: Chen, X.; Peng, G. J. Am. Chem. Soc., 1994, 116, 3127 'NC

N=PPh3 toluene, 75°C 14h

MeO1 OMe

/ MeO

wu

OBn

Ar = 3,4-dimethoxyphenyl

MeO Rodriques. J.A.R.: Leiva, G.C.; de Sousa, J.D.F. Tetrahedron Lett., 1995, 36, 59 phX^N^

Bn

(BnNEt3)2MoS4, MeCN, rt

| *" Ptt 00 Ilankumaran, P.; Chandrasekaran. S. Tetrahedron Lett., 1995, 36, 4881

1. Hg(OAc)2, aq. THF CgH17CH2N=C=O

+C8H17CH2NH2 2.NaBH 4) OHMalanga. C.: Urso, A.; Lardicci, L. Tetrahedron Lett., 1995, 36, 8859

quant.

Et3SiH, Ni(OAc)2«4 H2O

'OH Vetter, A.H.; Berkessel. A. Synthesis. 1995, 419

S

10% Yb(OTf)3 , MeCN OMe

\ 74% Makioka, Y.; Shindo, T.; Taniguchi, Y.; Takaki. K.: Fujiwara, Y. Synthesis, 1995, 801

Section 105

Amines from Azides

135

BER-Ni(OAc)2, MeOH , 75°C *PhCH2NH2 BER = borohydride exchange resin Bandgar. B.P.: Nikat, S.M.; Wadgaonkar, P.P. Synth. Commun., 1995, 25, 863 PhCH=N-OH

l.Ac£)

J-OH _ ,, Me

)

•-

2. NaBH4,12

NH2

/ Me

Barbrv. P.: Champagne, P. Synth. Commun., 1995, 25, 3503 Cp2MoH2, toluene '

-N" H

Minato, M.; Fujiwara, Y.; Ito. T. Chem. Lett., 1995, 647 Ph

\ V==N.-Bn

Me'

'

Ph

BnNH2, H 2 , Ir(R-BINAP)

}

*•

MeOH

N-Bn

Me

quant. (66% ee, S) Tani. K.: Onouchi, J.; Yamagata, T.; Kataoka, Y. Chem. Lett., 1995, 955

AMINES FROM AZIDES BER-Ni(OAc)2, MeOH rt, 30 min

BER = borohydride exchange resin Yoon. N.M.! Choi, J.; Shon, Y.S. Synth. Commun., 1993, 23, 3047 BuN3

NaBH4. cat. CuS04, MeOH

^

Ri^

95%

Rao. H.S.P.: Siva, P. Synth. Commun., 1994, 24, 549 SmI2,THF

H2N 96% Benati. L.: Montevecchi, P.C.; Nanni, P.; Spagnolo, P.; Volta, M. Tetrahedron Lett., 1995, 36, 7313

136

Compendium of Organic Synthetic Methods, Vol 9

^\

LiMe2NBH3 , THF, 0°C

^J~^

Section 105

^\ ~

[^-NH2

90%

Alvarez, S.G.; Fisher, G.B.; Singaram. B. Tetrahedron Lett., 1995, 36, 2567 2.5SmI 2 ,THF,rt,lh CioH2i—NS »CioH2i—NH2 Goulaouic-Dubois, C.; Hesse. M. Tetrahedron Lett., 1995, 36, 7427 BHCl2-SMe2, CH2C12

35%

^^ 95%

Salunkhe, A.M.; Brown. H.C. Tetrahedron Lett., 1995, 36, 7987 AMINES FROM NITRO COMPOUNDS

P 1. 7 eq. SmI2, THF/MeOH rt, Id 2. oxalic acid/water 95% (6:1 trans:cis) Sturyess. M.A.: Yarberry, DJ. Tetrahedron Lett., 1993, 34, 4743 NO2

hv, TiO2 EtOH

Mahdavi, F.; Bruton, T.C.; Li. Y. J. Org. Chem., 1993, 58, 744 borohydride exchange resin NH2

Ni(OAc)2, MeOH , rt, 30 min

94%

Yoon. N.M.: Choi, J. Synlett, 1993, 135 NOz

Baker's yeast, NaOH aq. MeOH , 80°C , 4h

NH2

Br "^ Br Baik. W.: Han, J.L.; Lee, K.C.; Lee, N.H.; Kim, B.H.; Hahn, J.-T. Tetrahedron Lett., 1994, 35, 3965

Section 105 A

Protection of Amines

137

. CuBr«SMe2 , NaBH4 , THF

^ 2. MeOH, 10°C Patel. H.V.: Vyas, K.A. Org. Prep. Proceed. Int., 1995, 27, 81

PhNH2

H2N-NMe2, FeCl3 , MeOH, 18h

<\

/)

"02

*-

<X

/>

NH2

89%

Boothroud, S.R.; Kerr. M.A. Tetrahedron Lett., 1995, 36, 2411

, 2h PhNO2 -*PhNH2 Ren, P.-D.; Pan, S.-F.; Dong, T.-W.; Wu. S.H. Synth. Commun., 1995, 25, 3799

86%

EtOH, 30 min Gohain, S.; Prajapati, D.; Sandhu. T.S Chem. Lett., 1995, 725 REVIEWS: "Asymmetric Reductions of C-N Double Bonds. A Review," Zhu, Q.-C.; Hutchins. R.O. Org. Prep. Proceed. Int., 1994, 26, 193 "Reduction of Nitro-Substituted Tertiary Alkanes," Weis, C.D.: Newkome. G.R. Synthesis. 1995, 1053

SECTION 105A: PROTECTION OF AMINES

CO2Me

(FMoc)NH"

"V"

"V^

KF , NEt3 , DMF 1

BocaO.rt.lOh

(f-Boc)NH

85% Li, W-R.; Jiang, J.; Joullid, M.M. Tetrahedron Lett., 1993, 34, 1413

| ^^

Pd(OAc)2 + TPPTS , Et2NH -M r N J O .-aq. MeCN , 9 mm

72% also with carbonates to give alcohols Genet. J.P.: Blart, E.; Savignac, M.; Lemeune, S.; Paris, J.-M. Tetrahedron Lett., 1993, 34, 4189

138

Compendium of Organic Synthetic Methods, Vol 9

Section 105 A

1. TMSI, HMDS , MeCN . 2. DABCO 3. HC1, H2O

o CC^H Fisher. J.W.: Dunigan, J.M.; Hatfield, L.D.; Hoying, R.C.; Ray, I.E.; Thomas, K.L. Tetrahedron Lett., 1993, 34, 4755 Pd(PPh3)4 , NDMBA, 30°C CH2Q2,1.5h *-

NDMBA = N.N-dimethylbarbituric acid Garro-Helion, F.; Merzouk, A.; Guibe, F. J. Org. Chem., 1993, 58, 6109

^^^ PIT NH2 quant

NHBoc

quant. Gibson, F.S.; Bergmeier, S.C.; Rapoport. H. 7. Org. Chem., 1994, 59, 3216 SmI2 , THF , DMPU , reflux -:-^ 4.5h Vedeis. E.: Lin, S. 7. Org. Chem., 1994, 59, 1602 Pd(dba)2, dppb, 20°C, 25 min 2-(SH)C6H4COOH, THF

Bn;N—H

pnx^^ N Me

quant. Lemaire-Audoire, S.; Savignac, M.; Genet J.P.: Bernard, J.-M. Tetrahedron Lett., 1995, 36, 1267 J

^\ NHTFA MeHN ^^ selective for 1° amines >95% Xu, D.; Prasad. K.: Repic, O.; Blacklock, TJ. Tetrahedron Lett., 1995, 36, 7357 MeHN'

^^

,NH2

^

'

'

*"

92%

Section 105 A

Protection of Amines

Q

139

Cl

, DCE, reflux Me

2. MeOH , reflux Bn Yanp. B.V.: O'Rourke, D.; Li, J. Synlett, 1993, 195 TiCls-Li , THF , reflux , 22h ^ Talukdar, S.; Banerji. A. Svnth. Commun., 1995, 25, 813

Me2NH

55%

140

Compendium of Organic Synthetic Methods, Vol 9

Section 107

CHAPTER 8 PREPARATION OF ESTERS

SECTION 106: ESTERS FROM ALKYNES QH _ EEEE

—

—

OEt

OH I

xylenes , 150°C

-

—

72%

OH Liang, L.; Ramaseshan, M.; MaGee. D.I. Tetrahedron, 1993, 49, 2159

SECTION 107: ESTERS FROM ACID DERIVATIVES The following types of reactions are found in this section: 1. 2. 3.

Esters from the reaction of alcohols with carboxylic acids, acid halides and anhydrides. Lactones from hydroxy acids Esters from carboxylic acids and halides, sulfoxides and miscellaneous compounds

Li [Binol-AlHOEt] , THF -78°C -» rt

"O Matsnki. K.: Inoue, H.; Takeda, M. Tetrahedron Lett., 1993, 34, 1167 PhCH2OH, 2,6-lutidine 'C1 ,CH2C12

\ ^

Fohner, J J.; Weinreb. S.M. Tetrahedron Lett., 1993, 34, 2737

81%

Section 107

Esters from Acids

141

^^ O I / 2

H\

90 C OH ° ^^ ^V^ ><JifiPrt, 93% Soderquist. J.A.: Miranda, E.I. Tetrahedron Lett., 1993, 34, 4905

O2H

3 eq. TEOA, 24h 110°C,Tol

92%

TEOA = triethyl orthoacetate Trujillo, J.I.; Gopalan. A.S. Tetrahedron Lett., 1993, 34, 7355 C8H l7 OH,TsOH,neat PhCO2H

*• PhCO2C8H17 97% microwave, 3 min Loupy. A.: Petit, A.; Ramdani, M.; Yvanaeff, C.; Majoub, M.; Labiad, B.; Villemin. D. Can. J. Chem., 1993, 71, 90 l.NBS CH2C12,MS4A 0°C,PPh 3

^x\ PbT ^C02H

^^^ O. ph PlT^tf^^^^

*98% 2. PhCH2OH, Py, Ih ™ Q Sucheta, K.; Reddy, G.S.R.; Ravi, D.; Ramo Rao. N. Tetrahedron Lett., 1994, 35, 4415

Ph

^^

OH

20%TiCl4 + 2AgClO4 (ArCO)2O, MS3A AT = 3,5-trifluoromethylphenyl Shiina, I.; Miyoshi, So.; Miyashita, M.; Mukaiyama, T. Chem. Lett., 1994, 515 5%TiCL2(OTf)2,(ArCO)2O 3 TMSC1, CH2C12 (2 mM)

n

[| HO

(CH2)io

OH

reflux (slow addition over 5 h)

AT = 4-trifluoromethylphenyl Shiina, I.; Mukaiyama, T. Chem. Lett., 1994, 677

o

/\_ (CH2)10 83% + 10% diolide

142

Compendium of Organic Synthetic Methods, Vol 9

Q

Section 108

O

1.6eq. C17H3iCOOH cat. DMAP, Ih 85% Takeda. K.: Akiyama, A.; Konda, Y.; Takayanagi, H.; Harigaya, Y. Tetrahedron Lett., 1995, 36, 113

I. PhI(02CCF3)2

I

I

N~

2.12, hv

CO2H

Togo. H.: Muraki, T.; Yokovama. M. Tetrahedron Lett., 1995, 36, 7089 ,CO2H

, 100°C, 5 eq. NEt3 5% Pd(PPh3)4, ZnCl2

Liao, H.-Y.; Cheng. E.H. J. Org. Chem., 1995, 60, 3711 Further examples of the reaction RCO2H + R'OH -> RCO2R1 are included in Section 108 (Esters from Alcohols and Phenols) and in Section 30A (Protection of Carboxylic Acids).

SECTION 108: ESTERS FROM ALCOHOLS AND THIOLS Further examples of the reaction ROH —> RCO2R' are included in Section 107 (Esters from Acid Derivatives) and in Section 45 A (Protection of Alcohols and Phenols). l.BuLi,THF,rt 2. Ph3B , rt k

OH

(80:20 E:Z) 10% PPh3, reflux Stary, I,; Stara\ I.G.; Kocovsky, P. Tetrahedron Lett., 1993, 34, 179

40%

Section 108

Esters from Alcohols

143

« f^Yco^A

' ^ ^J°2Me

35CafOCn, 2AcOH j.j v^«^v/v^i^2 » ~ /\vv/n.

!89% 32MeOH,dark,2d "*" I J MeCN, rt ^^^ McDonald. C.E.: Nice, L.E.; Shaw, A.W.; Nestor, N.B. Tetrahedron Lett., 1993, 34, 2741

1. SOC12, DMF C13H27CH2OCHO 2.H20 Fernandez, I.; Garcia, B.; Munoz, S.; Pedro. J.R.: de la Salud, R. Synlett, 1993, 489

95%

KNOyBF3»1.25 H2O CH2C12 , 0°C -* rt

95%

Olah. G.A.: Wang, Q.; Li, X.; Prakash, G.K.S. Synthesis, 1993, 207

1. Cr(CO)5-THF, THE, 55°C OH

2 CAN

'

" 81%

Quavle. P.: Rahman, S.; Ward, E.L.M. Tetrahedron Lett., 1994, 35, 3801

Pb(OAc)4, PhH, CO 'OH

40°C, Id

*" 51%

Tsunoi, S.; Rvu. I.: Sonoda. N../. Am. Chem. Soc., 1994, 116, 5473 NaBrO2, A12O3, CH2C12

Morimoto. T.: Hirano, M.; Iwasaki, K.; Ishikawa, T. Chem. Lett., 1994, 53 MeC(OEt)3 , EtCO2H , DMF microwave, 12 min Srikrishna. A.: Nagaraju, S.; Kondaiah, P. Tetrahedron, 1995, 51, 1809

63% -CC^Et

144

Compendium of Organic Synthetic Methods, Vol 9

Section 109

02CAr TMAD, DEAD, Bu 3 P, PhH 4-(MeO)C6H4COOH , 60°C, Id

TMAD = Me2NCON=NCONMe2 A Mitsunobu reaction for sterically hindered alcohols 93% Tsudoda. T.: Yamamiya, Y.; Kawamura, Y.; Ito, S. Tetrahedron Lett., 1995, 36, 2529 OH

3 eq. NCS , CH2C12, 20°C , 5h

• OH

Kondo. S.: Kawasoe, S.; Kunisada, H.; Yuki, Y. Synth. Commun., 1995, 25, 719 NaBrO3 , NaHSO3 , H2O OH

rt,2h 76% Takase, K.; Masuda, H.; Kai, O.; Nishiyama, Y.; Sakaguchi, S.; Ishii. Y. Chem. Lett., 1995, 871

SECTION 109: ESTERS FROM ALDEHYDES 2:MOMCl,iPr2NEt ^^^^^^

T> j|

3.O3,CH2C12,-78°C (quant.) Linderman. R.J.: Jaber, M. Tetrahedron Lett., 1994, 35, 5993 CHO

mcpba, CH2C12, it, 2.5h

OMe Alcaide. B.: Aly, M.F.; Sierra, M.A. Tetrahedron Lett., 1995, 36, 3401

OMe

Section 111

Esters from Amides

145

1% Cu(OAc)2«4 H2O, O2, DCE 3 iPrCHO

|

^

87%

OMe

A™ OMe Anoune, N.; Lant6ri, P.; Longeray, R.; Arnaud. C. Tetrahedron Lett., 1995, 36, 6679

PhCHO

PhI(OAc)2 , NaN3, PhSSPh

Ph CH2Cl2,rt ^SPh Tineoli. M.: Temperini, A.; Testaferri, L.; Tiecco, M. Synlett, 1995, 1129

Ac2p, HY zeolite, CC14 PhCHO

62%

,OAc -

Ph


9g%

OAc Pereira, C.; Gigante. B.: Marcelo-Curto, M.J.; Carreyre, H.; Pdrot, G.; Guisnet, M. Synthesis, 1995, 1077 Related Methods: Section 117 (Esters from Ketones) SECTION 110:

ESTERS FROM ALKYLS, METHYLENES AND ARYLS

No examples of the reaction R-R -» RCO2R' or R'CO2R (R,R' = alkyl, aryl, etc.) occur in the literature. For the reaction R-H —» RCO2R' or R'CO2R, see Section 116 (Esters from Hydrides). NO ADDITIONAL EXAMPLES SECTION 111: ESTERS FROM AMIDES

l.LiAlH 4 ,0°C

95%

2. TsOH , H2O , CH£12 25°C Canan Koch, S.S.; Chamberlin. A.R. J. Org. Chem., 1993, 58, 2725

146

Compendium of Organic Synthetic Methods, Vol 9

Section 113

TiCl4 , MeOH , 3h Ph,

NHOMe

^

"OMe

86% Fisher. L.E.: Caroon, J.M.; Stabler, S.R.; Lundberg, S.; Zaidi, S.; Sorensen, C.M.; Sparacino, M.L.; Muchowski, J.M. Can. J. Chem., 1994, 72, 142

oc<

N—Ph

1. BDMAB , Zn complex , -10°C 2. NaBH4

v O ° 69% (84% ee, 1R2S) Kang. J.: Lee, J.W.; Kim, J.I.; Pyun, C. Tetrahedron Lett., 1995, 36, 4265

^

^

SECTION 112: ESTERS FROM AMINES NO ADDITIONAL EXAMPLES SECTION 113: ESTERS FROM ESTERS Conjugate reductions and conjugate alkylations of unsaturated esters are found in Section 74 (Alkyls from Alkenes). l.N2CHCO2Et,CH2C!2 Rh2(OAc)4 Me2SiClH

*(iPrO)Me2SiCH2CO^t 2.iPrOH,NEt 3 Andrey, O.; Landais. Y.: Panchenault, D. Tetrahedron Lett., 1993, 34, 2927 10% TiCl4, 2 AgClO4, CH2C12 =O

(CH2)10 ^OSiMe3

(ArCO2)2O, it, 3 hr addition

AT - 4-trifluoromethylphenyl Mukaiyama, T.; Izumi, J.; Miyashita, M.; Shiina, I. Chem. Lett., 1993, 907

75%

!.LDA,Me3siCl ^ 2 H2Se

*OMe " Wright. S.W. Tetrahedron Lett., 1994, 35, 1331

_.

II

74%

Section 113

Esters from Esters

147

81% + 14% diolide II

O

[ with BuSnH/AIBN -» 70% lactone + 0% diolide ] White. J.D.: Green, N.J.; Fleming, F.F. Tetrahedron Lett., 1993, 34, 3515 2.5% [Pd(n'-C3H5)C.]2 CH2C12, 36h , CH2(CO2Me)2 PI

BSA,AcOK,rt

M£O^

^'

6%

BSA = N,O-to-(trimethylsilyl)acetamide

\L./

(89% ee,S) Kubota, H.; Nakajima, M.; Koga. K. Tetrahedron Lett., 1993, 34, 8135

O CO2Et TMSC1 , Nal , MeCN

82%

Tetrahedron, 1994, 50, 13687 hv , NaBH3CN, MeOH I—(H£)io, 3h,rt

>^

) 83x74%

Abe, M.; Hayashikoshi, T.: Kurata. T. Chem. Lett., 1994, 1789

h [Rh2(OAc)4]

O 46% (40:60 cis:trans) Miiller. P.: Polleux, P. Helv. Chim. Acta, 1994, 77, 645

148

Compendium of Organic Synthetic Methods, Vol 9

,-v / i

X

V x^^^

l.LDA.THF 2.BnBf,THF,-78°C

Section 114

^B -

3. satd. NH£1 , -78°C

83% (10:1 anti:syn) Anceau, C.; Dauphin, G.; Coudert, G.; Guillaumet. G. Bull. Soc. Chim. Fr., 1994, 131, 291 3 BuCHO , 3 Mg , 3 TMSC1 'CO2Et

DMF

Ohno, T.; Ishino, Y.; Tsumagari, Y.; Nishiguchi. I. J. Org. Chem., 1995, 60, 458

J

/

'I

CO Bn

V^21J11 2

chiral Ti complex , I 2 , CuO

(CH2)3-/

CH2C12,13h H

quant (76% ee) Inoue, T.; Kitagawa, O.; Kurumizawa, S.; Ochiai, O.; Taguchi. T. Tetrahedron Lett., 1995, 36, 1479

2 eq. In, DMF

62%

Schick. H.: Ludwig, R.; Kleiner, K.; Kunath, A. Tetrahedron, 1995, 51, 2939

SECTION 114:

ESTERS FROM ETHERS, EPOXIDES AND THIOETHERS 1.5 AcBr,5%SnBr 2

Orivama. T.: Oda, M.; Gono, J.; Koga, G. Tetrahedron Lett., 1994, 35, 2027

Section 115

Esters from Halides

O

149

TS-1, 55%

TS-1 = titanium silicate O Sasidharan, M.; Suresh, S.; Sudalai. A. Tetrahedron Lett., 1995, 36, 9071 PhCH2CH2OCH2Ph

SnBrrAcBr, CH2C12

^

PhCH2CH2OAc

rt.lh

92%

Orivama. T.: Kimura, M.; Oda, M.; Koga, G. Synlett, 1993, 437 P.T,

J^JD U

NdBrs, AcOH, microwave

^A,,

A_/y\C

Ph

Ph

—^ 1.7 min Yulin, J.; Yuncheng, Y. Synth. Commun., 1994, 24, 1045

~~^2%

PdCl2-CuCl2, C^, acetone

pn'

^

^.Ph ^

V

^

CO(60atm), 2d 16% O Miyamoto, M.; Minami, Y.; Ukaji. Y.: Kinoshita, H.: Inomata. K. Chem. Lett., 1994, 1149 /

\^

67 atm CO, 180°C, PhH. 2d

„

/

\^

0

73%

C 2Et

^S^^ ^ [Rh(cod)Cl]2 ^S^ ° Khumtaveeporn, K.; Alper. H. J. Chem. Soc. Chem. Commun., 1995, 917

SECTION 115: ESTERS FROM HALIDES AND SULFONATES l.(MeS)£Li,THF,-78°C BuBr

*BuCOSMe 91x84% 2. 35% aq. HBF4 , THE , 70°C Barbero, M.; Cadamuro, S.; Degani. I.: Dughera, S.: Fochi. R. J. Chem. Soc., Perkin Trans. 1., 1993, 2075 Cl

CO2Et

CH2C12,0°C -> 20°C Bott. K. Tetrahedron Lett., 1994, 35, 555

PK

cat. Bu4NNO3, NaNO3, PhH/H2O *• sealed tube (135°C)

Ph'

81% Hwu. J.R.: Yyas, K.A.; Patel, H.V.; Lin, C.-H.: Yang. J.-C. Synthesis. 1994, 471

150

Compendium of Organic Synthetic Methods, Vol 9

Section 116

Br

ArQK, CO, PdCl2(dppp). PhH 100°C p'

AT = 2,5-di-r-butyl-4-methylphenyl

"" r**^

84%

Ph Kubota, Y.; Hanaoka, T.-a.; Takeuchi, K.; Suei. Y. J. Chem. Soc. Chem. Commun., 1994, 1553

OMs

PhCH 2 H, CsF, DMF, 60°C

OBz

50% (100% ee)

Sato, T: Otera. J. Synlett. 1995, 336 Related Methods: Section 25 (Acid Derivatives from Halides).

SECTION 116: ESTERS FROM HYDRIDES This section contains examples of the reaction R-H -» RCO2R' or R'CO2R (R = alkyl, aryl, etc.). 5% Pd(OAc)2,1.5 H2O2 10% iuv0

u=

\\

u /* ' AcOH / 2h,50°C

77%

Akermark. B.: Larsson. E.M.: Oslob, J.D. J. Org. Chem., 1994, 59, 5729 PhCO3r-Bu , 5% CuOTf, 23°C MeCN,4d

-Y O

\

57% conversion 74% (74% ee)

Gokhale, A.S.; Minidis, A.B.E.; Pfaltz. A. Tetrahedron Lett., 1995, 36, 1831

Section 117

Esters from Ketones

RuCl3«n H 2 O, rt 2eq.MeCO3H TFA:CH^C12

-

/ ( \

\ ) /

151

02CCF3

+

/ ( \

\ )=0 /

69% 12% Murahashi. S.: Oda, Y.; Komiya, N.; Naota, T. Tetrahedron Lett., 1994, 35, 7953

5% chiral bis-oxazoline Cu complex PhCO2f-Bu , MeCN, -20°C 49%(81%ee) Andrus. M.B.: Argade, A.B.; Chen, X.; Pamment, M.G. Tetrahedron Lett., 1995, 36, 2945

o

Cu(OTf)2(chiral amine)3, PhCO3f-Bu rt, 40h

j___ OBz \

68% (74% ee, S)

/

Kawasaki, K.; Tsumura, S.; Katsuki. T. Synlett. 1995, 1245 /=^\ / \ \ /

2 eq. PhCO3r-Bu, 3 eq. PhCO3H *. PhH, 4h, 0.1 Cu2O , reflux, air

OBz

59% (45% ee, S)

Levina, A.; Muzart. J. Tetrahedron Asymmetry, 1995, 6, 147 Cu(OAc)2, S-proline, EtCO2H PhCO3r-Bu , 20°C, 16h 70% (57% ee) Rispens, M.T.; Zondervan, C.; Rispens, M.T.; Zondervan, C.; Feringa, B.L. Tetrahedron Asymmetry, 1995, 6, 661

Also via: Section 26 (Acid Derivatives) and Section 41 (Alcohols). SECTION 117: ESTERS FROM KETONES O2 (1 atm), 3 eq. PhCHO, 21h 0.2 Cu(OAc)2-H2O, DCE dark

I

^\^-

Bolm. C.: Schlingloff, G.; Weickhardt, K. Tetrahedron Lett., 1993, 34, 3405

f

94%

152

Compendium of Organic Synthetic Methods, Vol 9

THF, 25°C

Section 117

-CO2Me Ph

/

Ph 72% Cp Fennin, M.C.; Bnmo. J.W. Tetrahedron Lett., 1993, 34, 7545

e", SmCla, Mg anode

*

60%

Hebri, H.; Dunach, E.; Pgrichon, J. J. Chem. Soc. Chem. Commun., 1993, 499 MeOCO2Me, 195°C , K2CO3

P ^

6.4h

Ph

^v.

"N^^^ ^•^ ^n\>r OMe

71% Selva, M.; Marques, C.A.: Tundo. P. Gav. Chim. Ital., 1993, 123, 515 j -i

/

3 PhCHO , CC14

\=0

Kaneda. K.: Ueno, S.; Imanaka, T.; Shimotsuma, E.; Nishiyama, Y.; Ishii, Y. /. Org. Chem., 1994, 59, 2915

NBS, DME/H2O 0°C,30min

82% Marotta, E.; Piombi, B.; Righi, P.; Rosini. G. J. Org. Chem., 1994, 59, 7526 5.O

PhCHO , 5% MnO2

DCE, O2 , rt, Id

Inokuchi, T.; Kanazaki, M.; Sugimoto, T.; Torii. S. Synlett, 1994, 1037

Section 118

Esters from Nitriles

f^\

153

PhCHO,02,MgioAl2(OH)24C03

>=0

^-^X

-

/

\

\

/

(

DCE,40°C,5h

)=o

90%

Kaneda. K.: Ueno, S.; Imanaka, T. /. Chem. Soc. Chem. Commun., 1994, 797

OMe

OBn Chida, N.; Tobe, T.; Ogawa, S. Tetrahedron Lett., 1994, 35, 7249

_. Ph

OBn

O2, f-BuCHO, Cu complex I

-.

41%(65%ee)

Bolm. C.: Schlingloff, G.; Weickhardt, K. Angew. Chem. Int. Ed. Engi, 1994, 33, 1848 O

C«2,1% Cu complex r-BuCHO

(3[67%ee] : l[92%ee]) 61% Bolm. C.: Schlingloff, G. J. Chem. Soc. Chem. Commun., 1995, 1247 Also via: Section 27 (Acid Derivatives). SECTION 118: ESTERS FROM NITRILES cat. RuH2(PPh3)4, H2O

72% Naota, T.; Shichijo, Y.; Murahashi. S.-I. J. Chem. Soc. Chem. Commun., 1994, 1359

154

Compendium of Organic Synthetic Methods, Vol 9

Section 120

SECTION 119: ESTERS FROM ALKENES Me

Me

O3 , -78°C , MeOH/CH2Cl2

^13 Marshall. J.A.: Garofalo, A.W. J. Org. Chem., 1993, 58, 3675

63%

CO2Me

/

CH2(CO2Me)2, Mn(OAc)j

:O2Me

ultrasound

/=O

Allegretti, M.; D'Annibale, A.; Trogolo, C. Tetrahedron, 1993, 49, 10705 V2O5 , TFA, 70°C , 5h

Ci^if^^^^' ^^

n

*-

„

<-7Hl:>

86% Choudarv. B.M.: Reddy, P.N. J. Chem. Soc. Chem. Commun., 1993, 405

ICH2CO2Et,Cu,130°C

Metzger. J.Q.: Mahler, R. Angew. Chem. Int. Ed. Engl., 1995, 34, 902 Also via: Section 44 (Alcohols). SECTION 120:

ESTERS FROM MISCELLANEOUS COMPOUNDS

OSiMe2f-Bu

1. BuLi 2. CNCO2Me 44% 3. TBAF, THF 65% 4. Al/Hg , aq. THF 60%

Robin, S.; Huet. F. Tetrahedron Lett., 1993, 34, 2945

C^CCFS

Section 120

Esters from Misc.

155

CO, EtOH , iPr2NEt 2% Pd(PPh3)4,50°C 30atm . .. „ ,. (E:Z 84:16) 88% also works with allyhc acetates Murahashi. S.-L: Imada, Y.; Taniguchi, Y.; Higashiura, S. J. Org. Chem., 1993, 58, 1538 1. SmI2, HMPA , THF, f-BuOH reflux , Ih 2. H2Cr04

v

"

cr

/

/ (

.2

\

^cr 99%

Fukuzawa. S.: Tsuchimoto, T. Synlett, 1993, 803

, (Phco)2o

90% 20%TiCl4 + 2AgC104 OAc CH2C12 , it, 3h Miyashita, M.; Shiina. I.: Miyoshi, S.; Mukaiyama. T. Bull. Chem. Soc. Jpn., 1993, 66, 1516

OSiMe3

Me

Me3SiSN2,120°C DMEU, 18h

"~

N.

DMEU = l,3-dimethyl-2-imidazolidinone 63% Lai. L.-L.: Lin, R.Y.; Huang, W.-H.; Shiao, M.-J. Tetrahedron Lett., 1994, 35, 3545

156

Compendium of Organic Synthetic Methods, Vol. 9

Section 123

CHAPTER 9 PREPARATION OF ETHERS, EPOXIDES AND THIOETHERS

SECTION 121:

ETHERS, EPOXIDES AND THIOETHERS FROMALKYNES 1. Me3Si ==i MeCN, rt .„

Bu

2. NaOPh , MeOH

62% Kitamura. T.: Zheng, L.; Taniguchi, H.; Sakurai, M.; Tanaka, R. Tetrahedron Lett., 1993, 34, 4055

SECTION 122:

ETHERS, EPOXIDES AND THIOETHERS FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES

SECTION 123:

ETHERS, EPOXIDES AND THIOETHERS FROM ALCOHOLS AND THIOLS ©

© Br

NaOH , THF, rt, 5h Xu, C.; Lu, S.; Huang. X. Synth. Commun., 1993, 23, 2527 HO

1. Me3SiSSiMe3 2. BF3'OEt2,CH2Cl2

3. aq. NaHCO3 3 7 75% Tsav. S.-C.: Yep, G.L.; Chen, B.-L.; Lin, L.C.; Hwu, J.R. Tetrahedron, 1993, 49, 8969 C H

Section 123

Ethers from Alcohols

157

H

MeCOSH, h v , In

(2 : 1) 57% Kirpichenko. S V : Tolstikova, L.L; Suslova, E.N.; Voronkov, M.G. Tetrahedron Lett., 1993, 34, 3889

l.NaCNBH 3 ,Bu 3 SnCl AIBN , EtOH , reflux

H

CC13

2.NaOH,ether

Pl

67% (96%ee) Corev. E.J.: Helal, CJ. Tetrahedron Lett., 1993, 34, 5227

0 © S Na

CO(100bar),MeOH 150°C

^^^

^*f 98%

Bott. K. Chem. Ber., 1993, 126, 1955

PhCH2OH

PhCH2Cl , cety!Me3NBr , 5 min -*microwave

PhCH2OCH2Ph

85% Yuncheng, Y.; Yulin, J.; Jun, P.; Xiaohui, Z.; Conggui, Y. Gazz. Chim. Ital., 1993, 123, 519

OH SiMe^h

l.AlMe 3 ,CH 2 I 2 (67 % — 6:1 anti:syri) 2.p-TsOH (>30:1 (2,3-flnftVjyn)

, /

Panek. J.S.: Garbaccio, R.M.; Jain, N.F. Tetrahedron Lett., 1994, 35, 6453

BuOH, 0.2 M CAN reflux, 75 min OH Iranpoor. N.: Mothaghineghad, E. Tetrahedron, 1994, 50, 1859

92%

OBu

158

Compendium of Organic Synthetic Methods, Vol. 9

Section 124

1. ,6-di-r-butylpyridine, AgOTf CH2C12,0°C OH " 2. Mel 95%

Burk. R M.: Gac, T.S.; Roof, M.T.S. Tetrahedron Lett., 1994, 35, 8111 SPDBTQ

SPDBT 1. Hg(OAc)2, CH2C12 rt, 18h 2. aq. NaCl 3. BuaSnH, THF

i

*.

*.

,O

(7 : 1) 93% Garavelas, A.; Mavropoulos, I.; Perlmutter. P.: Westman, G. Tetrahedron Lett., 1995, 36, 463

5% Pd(OAc)2, DMSO , O2 23°C,ld

/*-^^-\ / H*5] \ 90%

Ronn, M.; Backvall, J.-E.; Andersson. P.G. Tetrahedron Lett., 1995, 36, 7749

OH

BnBr, Cs2CO3 , MeCN

*-

<\

/)

OBn

80°C ; Yuk, J.Y.; Cho, S.H. Synth. Commun., 1995, 25, 1367 OH

1. AC2O 2. (Cp)2TiMe2

80x80%

3. H 2 , Pd/C

Le Diguarher. T.: Billington, D.C.; Dorey, G. Synth. Commun., 1995, 25, 1633 SECTION 124: .CHO

ETHERS, EPOXIDES AND THIOETHERS FROM ALDEHYDES BuOH, Pd/C, H2 (40 bar), 100°C

wjth ketones Bethmont, V.; Fache, F.; LeMaire. M. Tetrahedron Lett., 1995, 36, 4235

DBu

Section 128

Ethers from Esters

159

PhCHO Et3SiH , TMSOTf, CH2C12, -30°C -» 0°C

99% Hatakevama. S.: Mori, H.; Kitano, K.; Yamada, H.; Nishizawa. M. Tetrahedron Lett., 1994, 35, 4367

\

/

Al(OAr)3 , -78°C , Ih

AT = 2,5-diphenylphenyl Maruoka, K.; Concepcion, A.B.; Yamamoto. H. Synlett. 1994, 521

83%

©NTs Ar^Ss

,NaH,THF O ^ *H*j^| -5°C,ld ^ Pn< Baird, C.P.; Tavlor. P.C. J. Chem. Soc. Chem. Commun., 1995, 893 PhCHO

SECTION 125:

63%(70%ee)

ETHERS, EPOXIDES AND THIOETHERS FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES

SECTION 126:

ETHERS, EPOXIDES AND THIOETHERS FROM AMIDES NO ADDITIONAL EXAMPLES

SECTION 127:

ETHERS, EPOXIDES AND THIOETHERS FROM AMINES NO ADDITIONAL EXAMPLES

SECTION 128:

ETHERS, EPOXIDES AND THIOETHERS FROM ESTERS 1. Dibal, -78°C

Ph. —

2. TMSOTf, Py

^

Kivooka. S.: Shirouchi, M.; Kaneko, Y. Tetrahedron Lett., 1993, 34, 1491

91%

160

Compendium of Organic Synthetic Methods, Vol. 9

Section 129

1. 2 SmI2 , -30°C -» rt 2.A C2 0,DMAP,TEA CH2C12 84% (1.5:1) Molander. G.A.: McKie, J.A. J. Am. Chem. Soc., 1993, 115, 5821 PhSH.Pd2(dba)3.dppb THF.ld Goux, C.; Lhoste, P.; Sinou. D. Tetrahedron, 1994, 50, 10321

SECTION 129:

ETHERS, EPOXIDES AND THIOETHERS FROM ETHERS, EPOXIDES AND THIOETHERS 2 BF3-OEt2, CH2C12

/ ^ •"

/

\

OBn

V/>

OBn

Itoh, A.; Hirose, Y.; Kashiwagi, H.: Masaki. Y. Heterocvcles. 1994, 38, 2165 1. e', Ni (cyclam), DMF, 20°C Mg anode, C fiber cathode 2. H30+

^

'

-O

Olivero, S.; Clinet, J.C.; Dufiach, E. Tetrahedron Lett., 1995, 36, 4429 i

O Me,,,, / \ ^Ph ""/

1.2.5 f-BuLi,THF -100°C

Ph p-Tol—S\ 2.EICHO O Satoh. T.: Horiguchi. K. Tetrahedron Lett., 1995, 36, 8235

V

< OH

Ph 80%

NaBH£N , Bu3SnCl , AIBN OC12H25

9h

62%

Srikrishna. A.: Viswajanani, R. Synlett, 1995, 95

Section 132

Ethers from Ketones

Phi , 2% Pd(OAc>2 , 3 NEt3 6% PPh3 , DMF , 70°C

161

-o «"*

(>98

2) 66%

:

Killers, S.; Rieger. O. Synlett. 1995, 153 SECTION 130:

ETHERS, EPOXIDES AND THIOETHERS FROM HALIDES AND SULFONATES

BER-PhSSPh , MeOH , reflux CgHnBr -Yoon. N.M.: Choi, J.; Ahn, J.H. J. Org. Chem., 1994, 59, 3490

CgH17—S—Ph

96%

MeSCH2Cl , A1C13 CH2C12,0°C Olah. G.A.: Wang, Q.; Neyer, G. Synthesis, 1994, 276 PhSH, rt V

^-

I

V

Lee, S.B.; Hong. J.-I. Tetrahedron Lett., 1995, 36, 8439 Related Methods: Section 123 (Ethers from Alcohols). SECTION 131:

ETHERS, EPOXIDES AND THIOETHERS FROM HYDRIDES

.SPh OMe

PhSH, (CF3)^CHOH PIFA.rt

PIFA = phenyliodine(in) fow(trifluoroacetate) Kita. Y.: Takada, T.; Mihara, S.; Tohma, H. Synlett, 1995, 211 SECTION 132:

ETHERS, EPOXIDES AND THIOETHERS FROM KETONES BusSnH, AIBN PhH(O.OSM)

\

J

76%

'Me Tsai. Y-M.: Tang, K-H.; Jiaang, W-T. Tetrahedron Lett., 1993, 34, 1303

162

Compendium of Organic Synthetic Methods, Vol. 9

A

X\/SiMe3

Section 134

<S^^

50% ^1^ *" 1 p. TBAF >\ ™ PIT Ph Capperucci, A.; Degl'Innocenti. A.: Ferrara, M.C.; Bonini, B.F.; Mazzanti, G.; Zanti, P.; Ricci, A. Tetrahedron Lett., 1994, 35, 161

OAc / , Rh2(OAc)4 PhF , 10 h

L

J^

.

•o

Pirrung. M.C.: Lee, Y.R. Tetrahedron Lett., 1994, 35, 6231 Related Methods: Section 124 (Epoxides from Aldehydes). SECTION 133:

ETHERS, EPOXIDES AND THIOETHERS FROM NITRILES NO ADDITIONAL EXAMPLES

SECTION 134:

ETHERS, EPOXIDES AND THIOETHERS FROM ALKENES Asymmetric Epoxidation , NaOd

/\

Mn-salen derivative 0°C , pH 11.3

\

N

/ -''

\

C02Et

(77% ee)

Chang, S.; Lee, N.H.; Jacohsen. E.N. / Org. Chem., 1993, 58, 6939 Mn (salen) catalyst , Ih

^X7^ ^/^\

0

1%H2O2,0 C,CH2C12 Schwenkreis, T.; Berkessel. A. Tetrahedron Lett., 1993, 34, 4785

77% (64%ee)

Section 134

Ethers from Alkenes

// Ph

*

163

threitol-strapped Mn-porphyrin, CH2p2 "" iodosylbenzene, 1,5-dicyclohexylimidazole

A Ph

^—O

86% (69% ee, R+) Collman. J.P.: Lee, V.J.; Zhang, X.; Ibers, J.A.; Brauman, J.I. J. Am. Chem. Soc., 1993, 115, 3834

chloroperoxidase, acetone

O

78% (96%ee,2R3S) Allain, E.J.; Hager. L.P.: Deng, L.; Jacobsen, E.N. J. Am. Chem. Soc., 1993, 115, 4415 Ph

B— OMe

f-BuOOH 35% (22% ee, S,S) Manoury, E.; Mouloud, H.A.H.; Balavoine. G.G.A. Tetrahedron Asymmetry, 1993, 4, 2339

Mn salen catalyst, C>2 PhH.rt 51% (52% ee) Mukaiyama, T.; Yamada, T.; Nagata, T.; Imagawa, K. Chem. Lett., 1993, 327

Ph

ru

Ph—<\

© 0 N-0

^

cat. Mn salen , 0°C, buffered bleach, pHl 1.3

pn

Ph

w

69% (93% ee, S,S)

Brandes, B.D.; Jacobsen. E.N. J. Org. Chem., 1994, 59, 4378 cat Mn(salen), CH2C12 •"

Pietikainen. P. Tetrahedron Lett., 1994, 35, 941

P!K .xix. s ^ \l 49% O (42%ee, 1S.2S)

164

Compendium of Organic Synthetic Methods, Vol. 9

Section 134

Mn salen catalyst, PhIO, 0°C

~* I JL/ •o 72% (98% ee)

Sasaki, H.; Irie, R.: Katsuki. T. Svnlett. 1994, 356 2 PhIO, Mn salen catalyst

pn

O

rt

27% (15% ee, 1R2R) Sasaki,H.; Irie, R.; Hamada, T.; Suzuki, K.; Katsuki. T. Tetrahedron, 1994, 50, 11827

Mn salen catalyst, r-BuCHO O 2 ,rt 28% (63:37 cis:trans) 80% ee for cis Nagata, T.; Imagawa, K.; Yamada, T.; Mukaiyama, T. Chem. Lett., 1994, 1259 O2, Mn salen complex, rt NMI, pivaladehyde, PhF

78% (63% ee) Yamada. T.: Imagawa, K.; Nagata, T.; Mukaiyama, T. Bull Chem. Soc. Jpn., 1994, 67, 2248

Mn (salen) catalyst, „.Ph

imidazole, rt, 3h

_.., Pn 53% (47% ee, 1R.2S (-))

Pietikainen. P. Tetrahedron Lett., 1995, 36, 319 20% 4-Ph-pyridine N-oxide, 0°C 5% Mn salen complex , CH2C12 ^^s.

/

Q

37% 35% ee

Brandes, B.D.; Jacobsen. E.N. Tetrahedron Lett., 1995, 36, 5123

Section 134

Ethers from Alkenes

165

8% Mn salen complex, mcpba, NMO ^^^

PIT

CH2C12, -78°C 89% (86% ee) Palucki, M.; McCormick, G.J.; Jacobsen. E.N. Tetrahedron Lett., 1995, 36, 5457

. Ph

"

chloroperoxidase, KOAc, H2O2 antifoam A , aq. acetone, pH 5.2 sodium citrate

Ph

'"

O

89% (49% ee) Dexter, A.F.; Lakner, F.J.; Campbell, R.A.; Hager. L.P. J. Am. Chem. Soc., 1995, 117, 6412

, Mn salen catalyst, f-BuCHO

70% (64% ee) Nagata. T.: Imagawa, K.; Yamada, T.; Mukaiyama, T. Bull Chem. Soc. Jpn., 1995, 68, 1455

Non-Asymmetric Epoxidation BIPA, FeCl2,02

22%

70°C, Id BIPA = N,N'-bis{2-(4-imidazoloyl)ethyl}-2,6-pyridinecarboxamide ; Moriuchi, T.; Mikami, S.; Ikeda, I.; Ohshiro, Y. Tetrahedron Lett., 1993, 34, 1031 cat. [K-10-montmorilloniteNi(acac)] iBuCHO , CH2C12 , rt autoclave, 10 bar Bouhlel, E.; Laszlo. P.: Levart, M.; Montaufier, M-T.; Singh, G.P. Tetrahedron Lett., 1993, 34, 1123 Laszlo. P.: Levart, M. Tetrahedron Lett., 1993, 34, 1127 [CoCl2/salicylaldehyde-L-serine methyl ester] 0 2 ,MeCN,rt,25h

"XT-

Punniyamurthy, T.; Bhatia, B.; Iqhal. J. Tetrahedron Lett., 1993, 34, 4657

166

Compendium of Organic Synthetic Methods, Vol. 9

Section 134

Fe cat.. O 2 , iPrCHO, rt

P Saalfrank. R.W.: Reihs, S.; Hug, M. Tetrahedron Lett., 1993, 34, 6033 10% O2 , DCE , 25°C , 4h -2 eq. iPrCHO 77% Hamamoto, M.; Nakayama, K.; Nishiyama, Y.: Ishii. Y. J. Org. Chem., 1993, 58, 6421

Co(mac)2, EtCH(OEt)2 97%

0 2 , M S 4 A , 4 5 ° C " /*\/ mac = 3-methyl-2,4-pentanedione Mukaiyama, T.; Yorozu, K.; Yakai, T.; Yamada, T. Chem. Lett., 1993, 439 Cu(OH)2 , CH3CHO , CH2C12 O2 , rt, 17h

79% Murahashi. S.-I.: Oda, Y.; Naota, T.; Komiya, N. /. Chem. Soc. Chem. Commun., 1993, 139

urea-H2O2 complex/maleic acid

O

Astudillo, L.; Galindo. A.: Gonzalez, A.G.; Mansilla, H. Heterocycles, 1993, 36, 1075 . [Mnm(TPP)(Cl)] , O

2. imidazole, BU4NIO4, 5h Mohajer. P.: Tangestaninejad, S. Tetrahedron Lett., 1994, 35, 945

H20/CH2C12 (pHll) lS-crown-6,5°C (9 : 91) 80% Kurihara. M.: Ito, S.; Tsutsumi, N.; Mivata. N. Tetrahedron Lett., 1994, 35, 1577

Section 134

Ethers from Alkenes

I ^^^^CLjs.

167

AgOAc/bipy/anode ACN (0.1 M LiCLO4)

H2 « ° O Kandzia, C.; Steckhan. E. Tetrahedron Lett., 1994, 35, 3695

"O

87% 87%

iPrCHO, Fe(AAEMA)3,02 rt,10h AAEMA =

"

O "

~

l

95%

O Mastrorilli, P.; Nobile. C.F. Tetrahedron Lett., 1994, 35, 4193

0

0

—

87%

™ H202 Kende. A.S.: Delair, P.; Blass, B.E. Tetrahedron Lett., 1994, 35, 8123

EtO

2. TBAF-3 H2O Capozzi. G.: Mecichetti, S.; Neri, S.: Skowronska. A. Svnlett. 1994, 267 i.

NaOCl, 4-methylpyridine

Ph—/

porphyrin catalyst/Mn Gonsalves. A.Md'A.R.: Pereira, M.M.; Serra, A.C.; Johnstone. R.A.W.: Nunes, M.L.P.G. 7. Chem. Soc., Perkin Trans. L, 1994, 2053 O2 (1 atm) , 2% Co(acac)2 EtCH(OEt)2,45°C,10h

o

48%

Yorozu. K.: Takai, T.; Yamada, T.; Mukaiyama, T. Bull. Chem. Soc. Jpn., 1994, 67, 2195

168

Compendium of Organic Synthetic Methods, Vol. 9

Section 134

Oxone, 0°C , Bu4NHSO4 acetone, CHjCLj, buffer

^^

^^

OBn

99%

Denmark. S.E.: Forbes, D.C.; Hays, D.S.; DePue, J.S.; Wilde, R.G. /. Org. Chem., 1995, 60, 1391 , MeCN, 0°C ^

15 min

-,. Me

,Q /—^

Ph

/ Me 96%

Yang. P.: Wong, M.-K.; Yip, Y.-C. J. Org. Chem., 1995, 60, 3887 ,C02H , methylene blue PhH,H 2 0

If

^T

"I

50%

Das. S.: Thanulingam, T.L.; Rajesh, C.S.; George, M.V. Tetrahedron Lett., 1995, 36, 1337 OH

H2O2 , DMF, pH 4-9 98%

Chen,Y.; Revmond. J.-L. Tetrahedron Lett., 1995, 36, 4015 f-BuOOH , Ti(OiPr)4 , SiO2 rt,ld

73% Fraile, J.M.; Garcia, J.I.; Mayoral. J.A.: de Menorval, L.C.; Rachdi, F. J. Chem. Soc. Chem. Commun., 1995, 539

PhIO, NaOCl, Mn salen catalyst *-

^^X^ ^1 92% ^ ^\' O Rasmussen, K.G.; Thomsen, D.S.; Jdrgensen. K.A. J. Chem. Soc., Perkin Trans. 1., 1995, 2009

Section 135

Ethers from Misc.

OH

169

f-BuOOH, MeOH CrS-2-molecular sieve

,,

Of/a

OJ%

Joseph, R.; Sasidharan, M.; Kumar. R.: Sudalai. A.: Ravindranathan. T. 7. Chem. Soc. Chem. Commun., 1995, 1341 Formation of Other Ethers PnSeSePh, CAN MeOH, 30 min

f

y^

93%

Bosman, C.; D'Annihale. A.: Resta, S.; Trogolo. C. Tetrahedron Lett., 1994, 35, 6525

C7H15

=

£

.CsHn

AgBF4 , acetone , rt 2h

OH

Marshall. J.A.: Sehon, C.A. 7. Org. Chem., 1995, 60, 5966 REVIEW:

"Rational Design of Manganese-Salen Epoxidation Catalyts; Preliminary Results," Hosoya, N.; Hatayama, A.; Irie, R.; Sasaki, H.; Katsuki. T. Tetrahedron, 1994, 50, 4311 SECTION 135:

ETHERS, EPOXIDES AND THIOETHERS FROM MISCELLANEOUS COMPOUNDS PhSSPh, SbCl5 , DCE •OMe

«reflux, 3h

PhS

^ \

/) ff

OMe 76%

Mukaiyama, T.; Suzuki, K. Chem. Lett., 1993, 1 LiAlH4, TiCl4 PhSO2Me ^ PhSMe 93% Akgiin, E.; Mahmoud, K.; Mathis. C.A. 7. Chem. Soc. Chem. Commun., 1994, 761

170

Compendium of Organic Synthetic Methods, Vol. 9

?

Section 135

[Si02/SOCl2] lOmin

/

\

73%

Mohanazadeh. F.: Momeni, A.R.; Ranjbar, Y. Tetrahedron Lett., 1994, 35, 6127

? ^S^

Cp2TiCl2, Sm , THF, rt

^

.s^*^ PIT Me

Phi Me Zhang. Y.: Yu, Y.; Bao, W. Synth. Commun., 1995, 25, 1825

||

TiCl4 , Sm, THF, rt, 30 min

Ph ^Ph Wang, J.Q.: Zhang. Y.M. Synth. Commun., 1995, 25, 3545

^,5

77-:

Section 138

Halides from Alcohols

171

CHAPTER 10 PREPARATION OF HALIDES AND SULFONATES

SECTION 136:

HALIDES AND SULFONATES FROM ALKYNES NO ADDITIONAL EXAMPLES

SECTION 137:

HALIDES AND SULFONATES FROM ACID DERIVATIVES PhIO , NBS , MeCN , 60°C *C02H

*"

73% (96:6 cis:trans) Graven, A.; Jorgensen. K.S.: Dahl, S.; Stanczak, A. J. Org. Chem., 1994, 59, 3543

SECTION 138:

HALIDES AND SULFONATES FROM ALCOHOLS AND THIOLS

PPh3, PhCH2OH *PhCH2Q Rivero, I.A.; Somanathan. R.: Hellberg, L.H. Synth. Commun., 1993, 23,111 «

95%

.Br

BBr3,CH2Cl2,0°C

quant. Pelletier, J.D.; Poirier. D. Tetrahedron Lett., 1994, 35, 1051 TMSC1 , DMSO Snyder. DC. ./. Org. Chem., 1995, 60, 2638

172

Compendium of Organic Synthetic Methods, Vol. 9

» P* ether, reflux, 1.5h

Section 142

42%

\—I

Joseph, R.; Pallan, P.S.; Sudalai, A.; Ravindranathan. T. Tetrahedron Lett., 1995, 36, 609

OH

Me3SiCl , BiCl3 _ • rt, n/\ 90 mm

//

*~l

quant, M

Labrouillere, M.; Le Roux, C.; Oussaid, A.; Gaspard-Iloughmane, H.; Dubac. J. Bull. Soc. Chim. Fr., 1995, 132, 522 REVIEWS: "An Alternative Synthesis of Aryl and Heteroaryl Bromides from Activated Hydroxy Compounds," Katritzkv. A.R.: Li, J.; Stevens, C.V.; Ager, D.J. Org. Prep. Proceed. Int., 1994, 26, 439 SECTION 139:

HALIDES AND SULFONATES FROM ALDEHYDES NO ADDITIONAL EXAMPLES

SECTION 140:

HALIDES AND SULFONATES FROM ALKYLS, METHYLENES AND ARYLS

For the conversion R-H —> R-Halogen, see Section 146 (Halides from Hydrides). 2eq.VO(OEt)Cl 2) N 2 MeCN,0°C->rt Fujii, T.; Hirao. T.: Ohshiro. Y. Tetrahedron Lett., 1993, 34, 5601 SECTION 141: HALIDES AND SULFONATES FROM AMIDES NO ADDITIONAL EXAMPLES SECTION 142: HALIDES AND SULFONATES FROM AMINES 1. TolSO2Cl 2. base 3. NBS , THF, hv

Collazo. L.R.: Guziec Jr., F.S.; Hu, W.-X.; Pankayatselvan, R. Tetrahedron Lett., 1994, 35, 7911

Section 146

Halides from Hydrides

173

SECTION 143: HALIDES AND SULFONATES FROM ESTERS NO ADDITIONAL EXAMPLES SECTION 144:

HALIDES AND SULFONATES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDITIONAL EXAMPLES

SECTION 145:

HALIDES AND SULFONATES FROM HALIDES AND SULFONATES n-CgHnl.KF.Cul + CO2 + MeCl CdI2 , HMPA , 120°C , 8h

Chen. Q.-Y.: Duan, J.-X. Tetrahedron Lett., 1993, 34, 4241 SECTION 146:

HALIDES AND SULFONATES FROM HYDRIDES

a-Halogenations of aldehydes, ketones and acids are found in Sections 338 (Halide-Aldehyde), 369 (Halide-Ketone), 359 (Halide-Esters) and 319 (HalideAcids). N02

BrF3, Br2 , 0*C

Rozen. S.: Lerman, O. J. Org. Chem., 1993, 58, 239

\ ^

/^OMe (/

CH2CI2 , MeOH

Bisarva. S.C.: Rao, R. Synth. Commun., 1993, 23, 779

\ /

NH2

PyH Br3 , THF

Reeves. W.P.: King II, R.M. Synth. Commun., 1993, 23, 855

174

Compendium of Organic Synthetic Methods, Vol. 9

Section 147

NBS/cat. HZSM-5 i\

/)

*-

OMe

Br

k

,)

OMe

^-^ ^ ^^ 70. 0^.28, Paul, V.; Sudalai, A.; Daniel, T.; Srinivasan. K.V. Tetrahedron Lett., 1994, 35, 7055

XeF2 , MeCN , 25°C , 6h

ff

H'

Wang, J.; Scott. A.I. Tetrahedron Lett., 1994, 35, 3679

NH4VO3, H2O2, KBr 2 phase (H2O/CHC13), 25°C

Br

Conte, V.; Pi Furia. F.: Moro, S. Tetrahedron Lett., 1994, 35, 7429 I 2 ,Hg(N03) 2 ,CH 2 Cl 2 20°C, 14h Bachki, A.; Foubelo, F.; Yus. M. Tetrahedron, 1994, 50, 5139 HgO-I2O,

Orito. K.: Hatakeyama, T.; Takeo, M.; Suginome, H. Synthesis, 1995, 1273 NBS , AcOH , ultrasound , 6h - Br

OMe

(v \

/) OMe / 92%

Paul, V.; Sudalai, A.; Daniel, T.: Srinivasan. K.V. Synth. Commun., 1995, 25, 2401 SECTION 147: 0

HALIDES AND SULFONATES FROM KETONES CF2Br2, Zn

Hu. C.-M.: Qing, F.-L.; Shen, C.-X. J. Chem. Soc., Perkin Trans. L, 1993, 335

58%

Section 150

Halides from Misc.

175

SECTION 148: HALIDES AND SULFONATES FROM NITRILES NO ADDITIONAL EXAMPLES SECTION 149:

HALIDES AND SULFONATES FROM ALKENES

For halocyclopropanations, see Section 74E (Alkyls from Alkenes). HC1, SiO2

i

\

•Cl

62% Krupp. P.J.: Daus, K.A.; Tubergen, M.W.; Kepler, K.D.; Wilson, V.P.; Craig, S.L.; Baillargeon, M.M.; Breton, G.W. J. Am. Chem. Soc., 1993, 115, 3071

KHF 2 ,SiF 4 ,rt

"F

'

79% Tamura. M.: Shibakami, M.; Kurosawa, S.; Arimura, T.; Sekiva. A. J. Chem. Soc. Chem. Commun., 1995, 1891 SECTION 150:

HALIDES AND SULFONATES FROM MISCELLANEOUS COMPOUNDS

O

l 2 ,CH 2 l2,80 0 C,4h

«~

Ph

1

>9g%

Wu, Z.; Moore. J.S. Tetrahedron Lett., 1994, 35, 5539

F 2 ,I 2 ) MeCN,rt

52% Chambers. R.D.: Sandford. G.: Atherton, M. J. Chem. Soc. Chem. Commun., 1995, 111 SOC12 , DMF, 100°C Ci2H25SO3Na *C^H^Cl 81% Carlsen, P.H.J.; Rist, 0.; Lund, T.; Helland, I. Acta Chem. Scand. B., 1995, 49, 701

176

Compendium of Organic Synthetic Methods, Vol. 9

Section 153

CHAPTER 11 PREPARATION OF HYDRIDES This chapter lists hydrogenolysis and related reactions by which functional groups are replaced by hydrogen: e.g. RCH2X -> RCH2-H or R-H.

SECTION 151: HYDRIDES FROM ALKYNES NO ADDITIONAL EXAMPLES SECTION 152: HYDRIDES FROM ACID DERIVATIVES This section lists examples of decarboxylations (RCO2H —» R-H) and related reactions.

NO ADDITIONAL EXAMPLES SECTION 153: HYDRIDES FROM ALCOHOLS AND THIOLS This section lists examples of the hydrogenolysis of alcohols and phenols (ROH —> R-H). 1. (Bu3Sn)£) , Tol , reflux , Id 2. 2 eq. EtNCO (90%) 3. Et3SiH , PhH , 140°C 0.05M , benzoyl peroxide (70%) Nishivama. K.: Oba, M.; Ishimi, M.; Sugawara, T.; Ueno, R. Tetrahedron Lett., 1993, 34, 3745 1. [PPVTfcOl , CH2C12 2.NaBH 4 ,rt_

^

3.1NHC1

8?%

Hendrickson. J.B.: Singer, M.; Hussonin, Md.S. J. Org. Chem., 1993, 58, 6913

Et3SiH, 3M LiClO4

." ^.

89%

ether HCT ^— "CO^t ^^ "CO2Et Wustrow. D.J.: Smith III, W.J.; Wise, L.D. Tetrahedron Lett., 1994, 35, 61

Section 157

Hydrides from Amines

TMSO f .X\IJ( I

177

3SmI 2 ,THF C6H13

V- C6H13

XXcf

XX

H H Linderman. R.J.: Cusack, K.P.; Kwochka, W.R. Tetrahedron Lett., 1994, 35, 1477

CH3—(CH2)9—OH

PPh3 , Et4NBr , MeCN -e"

CH3—(CH2)9—H

Maeda, H.; Maki, T.; Eguchi, K.; Koide, T.; Ohmori. H. Tetrahedron Lett., 1994, 35, 4129 l.MeCON=C=S

^ 48x83%

2. PhaSiH , AIBN , 80°C , 10 min Oba, M.; Nishivama. K. Synthesis, 1994, 624 Also via: Section 160 (Halides and Sulfonates). SECTION 154: HYDRIDES FROM ALDEHYDES For the conversion RCHO —> R-Me, etc., see Section 64 (Alkyls from Aldehydes). NO ADDITIONAL EXAMPLES

SECTION 155:

HYDRIDES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES

SECTION 156: HYDRIDES FROM AMIDES NO ADDITIONAL EXAMPLES SECTION 157: HYDRIDES FROM AMINES This section lists examples of the conversion RNH2 (or R2NH) —» R-H. NH2

, THF/H2O , 60% HNO3

Torii. S.: Okumoto, H.; Satoh, H.; Minoshima, T.; Kurozumi, S. Synlett, 1995, 439

67%

178

Compendium of Organic Synthetic Methods, Vol. 9

Section 158

SECTION 158: HYDRIDES FROM ESTERS This section lists examples of the reactions RCO2R1 -» R-H and RCO2R' -> R'H.

""HO

Pd(acac)2 , PBu3 , rt PhH.3h

92%

T^ "^

(alkynerallene = 99:1) Mandai. T.: Matsumoto, T.; Kawada, M.; Tsuii. J. Tetrahedron Lett., 1993, 34, 2161

SMe

hv

(tungsten lamp) Bu 3 SnH, 0°C

Me

1IiC

.. u other initiators were also used Barton, D.H.R.; Parekh. ST.: Tse, C.-L. Tetrahedron Lett., 1993, 34, 2733

5 eq. PhSiH3 , AIBN

<j

toluene, reflux, Ih quant.

Barton, D.H.R.; Jang, D.O.; Jaszverenyi, J.Cs. Tetrahedron, 1993, 49, 2793, 7193

,OPh

deoxygenated cyclohexane AIBN, 80°C

Gimisis, T.; Ballestri, M.; Ferreri, C.; Chatgilaloglu. C.: Boukherroub, R.; Manuel, G. Tetrahedron Lett., 1995, 36, 3897

Section 160

Hydrides from Halides

|AC

179

TBAF'x H 2 O, NMO, THF, rt 1,3-propanedithiol

Ph

*"

5 Uelo. M.: Okamura, A.; Yamaguchi, J. Tetrahedron Lett., 1995, 36, 7467

SECTION 159:

^V^^^ Ph II O 99%

HYDRIDES FROM ETHERS, EPOXIDES AND TfflOETHERS

This section lists examples of the reaction R-O-R' —> R-H. Sf-Bu

•Ph

TFA, 72°C, 1.5h \ Me Hamel. P.: Zajac, N.; Atkinson, J.G.; Girard, Y. Tetrahedron Lett., 1993, 34, 2059 5 eq. Ni2B , MeOH-THF CuH23-S-Ph

*-

2NiBr 2 + 6NaBH4

^

CnH24

90%

Ni2B

Back. T.G.: Baron, D.L.; Yang, K. /. Org. Chem., 1993, 58, 2407

DMN* , ascorbic acid, iPrOH Q

u

SePh

- I

I

>=0

hv ,3h

DMN* = photoactivated 1,5-dimethoxynaphthalene

o3%

Pandev. G.: Rao, K.S.S.P.; Sekhar, B.B.V.S. J. Chem. Soc. Chem. Commun., 1993, 1636 SECTION 160:

HYDRIDES FROM HALIDES AND SULFONATES

This section lists the reductions of halides and sulfonates, R-X -* R-H.

57%HI,25°C,15min

0

Br Penso. M.: Mottadelli, S.; Albanese, D. Synth. Commun., 1993, 23, 1385

9g%

180

Compendium of Organic Synthetic Methods, Vol. 9

Section 160

MeLi,THF,-105°C

52%

(98:2, E:Z) Grandjean, D.; Pale. P. Tetrahedron Lett., 1993, 34, 1155

Bu 3 SnH, AIBN, PhH reflux, 0.03M, 8h

OCH2CH2CH2Br CH2CH2CH2OH C3H7 an aryl translocation 24% 61% Lee. E.: Lee, C.; Tae, J.S.; Whang, H.S.; Li, K.S. Tetrahedron Lett., 1993, 34, 2343

NaBH2(OCH2CH2OMe)2 NiCl2, MeOCH2CH2OH THF, 68°C , 2h Cl Tabaei, S.H.; Pittman Jr.. C.U. Tetrahedron Lett., 1993, 34, 3263

HCO2H, Pd/C, toluene Cl

H2O, Na2CO3, 90°C quant.

Barren. J P: Baghel, S.S.; McCloskey, PJ. Synth. Commun., 1993, 23, 1601 Br

PVP-PdCl2,H2,65°C II

ambient pressure, EtOH , NaOH PVP-PdCl2= palladium anchored on poly(N-vinyl-2-pyrrolidinone) Zhang, Y.; Liao. S.: Xu, Y. Tetrahedron Lett., 1994, 35, 4599

'I

quant.

Section 162

„ __

Hydrides from Ketones

_

181

borohydride exchange resin, rt, 3h

LgH 17—Br

TT

»-

TT

CgH 17—H

0.1Ni(OAc)2,MeOH

quant.

Yoon. N.M.: Lee, H.J.; Ann, J.H.; Choi, J. J. Org. Chem., 1994, 59, 4687

:o2H

I 3.1 eq. Bu 3 SnH, AIBN H2O , 90°C , Id

Br Maitra. IT.: Sarma, K.D. Tetrahedron Lett., 1994, 35, 7861

SECTION 161: HYDRIDES FROM HYDRIDES NO ADDITIONAL EXAMPLES SECTION 162: HYDRIDES FROM KETONES This section lists examples of the reaction R2C-(C=O)R —> R2C-H. Et3SiH, BF3-OEt2, Ph Smonou. I Synth. Commun., 1994, 24, 1999

NaBHsCN , BF3OEt2 , THF H

°-\ \

:

/-\ ff \

rt,12h

^

H

° \\s ff /

94% Srikrishna. A.: Sattigeri, J.A.; Viswajanani, R.; Yelamaggad, C.V. Synlett, 1995, 93 H l.C!CO2Me 2, NaBH3

OH 94x76% Mitchell. P.: Doecke, C.W.; Hay, L.A.; Koenig, T.M.; Wirth, D.D. Tetrahedron Lett., 1995, 36, 5335

182

Compendium of Organic Synthetic Methods, Vol. 9

NHCOzMe

i.Me 3 SiCl,NEt 3

Section 165

NHCO2Me

2.Et3SiH,TiCl3 Yato, M.; Homma, K.: Ishida. A. Heterocvcles. 1995, 41, 17

NaCNBH3, THF BF3OEt2, ft, 30 min

MeO

MeO

(3 : 2) 85% Srikrishna. A.: Viswajanani, R.; Sattigeri, J.A.; Yelamaggad, C.V. Tetrahedron Lett., 1995, 36, 2347

SECTION 163: HYDRIDES FROM NITRILES This section lists examples of the reaction, R-C=N —> R-H (includes reactions of isonitriles (R-NsQ. SmI2,THF-HMPA,0°C

Ph

V

CN

*X f CN / H Ph Kang. H.-Y.: Hong, W.S.; Cho. Y.S.: Koh, H.Y. Tetrahedron Lett., 1995, 36, 7661

97%

Ph

SECTION 164: HYDRIDES FROM ALKENES NO ADDITIONAL EXAMPLES SECTION 165: HYDRIDES FROM MISCELLANEOUS COMPOUNDS ->H

Mg , EtOH, cat. HgCl2

it

Lee, G.H.; Choi, E.B.; Lee. E.: Pak. C.S. Tetrahedron Lett., 1993, 34, 4541

98%

Section 166

Ketones from Alkynes

183

CHAPTER 12 PREPARATION OF KETONES

SECTION 166: KETONES FROM ALKYNES 1. thxBHBfSMe 2 ,25°C, 12h 2. NaOH \

=

3. pH 7 buffer 4. H202 O Cha. J.S.: Min, S.J.; Kim, J.M.; Kwon, O.O. Tetrahedron Lett., 1993, 34, 5113

98 5%

CO-H2O, [Rh(COD)Cl]2 -SiMe3 NEt3,160°C , PPh3 , 4h Tekeuchi. R : Yasue, H. J. Org. Chem., 1993, 58, 5386

\

V

MeCN, 760°C, 4h •OMe

v

o

"""' (11:1,33%) Kim, O.K.; Wulff. W.D.: Jiang, W.; Ball, R.G. J. Org. Chem., 1993, 58, 5572 Me

^^

Ph

1.10% C02(CO)8 , DME 2.20% P(OPh)3 , reflux VYi

Iwasawa, N.; Matsuo, T. Chem. Lett., 1993, 997

91%

184

Compendium of Organic Synthetic Methods, Vol. 9

Section 167

1. Br2BH»SMe2 2. propylene glycol Br

Bu

3. CH2=CHCH2MgCl, THF, -78°C 4. HMPT, THF, 50°C, HMPA 5. oxidation Brown. H C: Soundararajan, R. Tetrahedron Lett., 1994, 35, 6963

Bu

95%

MeReO 3 ,H 2 O 2 ,tOH Ph

^=

Ph

Zhu, Z.; Espenson. J.H. J. Org. Chem., 1995, 60, 7728

SECTION 167: KETONES FROM ACID DERIVATIVES

ci

Ph

TiCLj-Zn, 3% HC1 Ph 69% 24% Shi, D.; Chen, J.; Chai, W.; Chen. W.: Kao, T. Tetrahedron Lett., 1993, 34, 2963

1. (C6H13)2Zn 2. CuCN«2 LiCl

Ph-"\,

98%

Langer, F.; Waas, J.; Knochel. P. Tetrahedron Lett., 1993, 34, 5261 e-,B U4 NBF4,rt

/^NX^

80%

meCN 6 O Folest. J.-C.: Pereira-Martins, E.; Troupel, M.; Perichon, J. Tetrahedron Lett., 1993, 34, 7571

1. (Me2N=CHCl)Cl, Py MeCN/THF ,CO2H ^ 2. 5 eq. NaN3 , 0°C 3.0°C -» rt Affandi, H.; Bayguen, A.V.; Read. R.W. Tetrahedron Lett., 1994, 35, 2729

Section 167

Ketones from Acids

185

Me(

CsH! iCOOH, (PhCO)2O , Id 20% (SiCl4 + 3 AgClO4) CH2C12, rt 67% MeO Suzuki. K.: Kitagawa, H.; Mukaivama. T. Bull. Chem. Soc. Jpn., 1993, 66, 3729 O

SnBu3 Pd(PPh3)4, dioxane 100°C , 30 h

II

..

ph

Ph'

o

Echavarren. A.M.: P6rez, M.; Castano, A.M.; Cuerva, J.M. J. Org. Chem., 1994, 59, 4179

l.(PhO)2PON3,NEt3 dioxane, reflux 2.2MHC1

61% (2.8:1 cis:trans) Booker-Milburn. K.I.: Cowell, J.K.; Harris, L.J. Tetrahedron Lett., 1994, 35, 3883

O J> -

f-BuCl/Li/ ultrasound

O 76% Aurell, M.J.; Einhorn, C.; Einhorn, J.; Luche. J.L. J. Org. Chem., 1995, 60, 8 0

O

iPrCl, Li, THF. ultrasound, rt

*•

Ph.

63% Aurell, M.J.; Danhui, Y.; Einhorn, J.; Einhorn, C.: Luche. J.L. Svnlett. 1995, 459

186

Compendium of Organic Synthetic Methods, Vol. 9

k

JOH

Q i,

NaIO4 , MeOH , TEBA *.

.xv

Section 168

92% CC^H DB-18-C6 Ph Ph— \ Kore, A.R.; Sagar, AD.; Salunkhe. M.M. Org. Prep. Proceed. Int., 1995, 27, 373 1

[Ph3GaBu]Li, THF-hexane, 0°C ^

Ph,

„ "

82%

'Cl Han, Y.; Fang, L.; Tao, W.-T.; Huang. Y.-Z. Tetrahedron Lett., 1995, 36, 1287

I

Cl

PhMgBr, CuBr, LiBr, THF, 0°C S

„ >^

^Ph

75%

O O Babudri, F.; Fiandanese, V.; Marchese. n.: Punzi, A. Tetrahedron Lett., 1995, 36, 7305

EtMgBr, Ni(dppe)Cl2

II

70%

x

THF Ph " " ' Malanga. C.: Aronica, L.A.; Lardicci, L. Tetrahedron Lett., 1995, 36, 9185

SECTION 168: KETONES FROM ALCOHOLS AND THIOLS 0.2% bis-Ru catalyst, THF 65°C C4H

BackvaU, J.-E.; Andreasson, U. Tetrahedron Lett., 1993, 34, 5459

2 DBU

' " 80x58% Antonioletti, R.; Arista, L.; Bonadies, F.; Locati, L.; Scettri. A. Tetrahedron Lett., 1993, 34, 7089 ,H

1. RuCl3-n H2O , CoCOAc)^ H2O EtOAc, CH3CHO , 20°C 2.1M Na2SO3

Murahashi. S.-L: Naota, T.; Hirai, N. J. Org. Chem., 1993, 58, 7318

Section 168

Ketones from Alcohols

187

0.05 CrO3 , 3 eq. 70% r-BuOOH Ph ^^ CH2C12, rt Muzart. J.I: Ajjou, A.N'A. Synthesis, 1993, 785

„

P

JL

1. Co(Imd)2, EtOAc Ph

2. imidazole, CH2C12

Ph

if

Ph

OH O Kang. S -K.: Park, D.-C.; Rho, H.-S.; Han, S.-M. Synth. Commun., 1993, 23, 2219 OH

PDC, Celite, CH2C12 25°C , Id X^^ 55%

Bijoy, P.; Subba Rao. G.S.R. Svnth. Commun., 1993, 23, 2701 PhI=O , Yb(NO3)3 , DCE 4h O aldehydes can also be formed quant. Yokoo, T.; Matsumoto, K.; Oshima. K.: Utimoto. K. Chem. Lett., 1993, 571

OH

, ZrO2 , toluene OH -- ( 110°C,6h

>=0

aldehydes can also be formed Nakamura, H.; Matsuhashi, H.; Arata, K. Chem. Lett., 1993, 749 5% CoSANSE, MeCN 60-70°C , O2 ,17h "OH CoSANSE = [bis(sah'cylidene-N-(methyl-3-hydroxypropionate))] Co Punniyamurthy, T.; Iqhal. J. Tetrahedron Lett., 1994, 35, 4007

'O

72%

188

Compendium of Organic Synthetic Methods, Vol. 9

Section 168

Phi , 3% Pd(OAc)2 , DMF 3 eq. KOAc , 80°C , 3d

_

Larock. R.C.: Yum, E.K.; Yang, H. Tetrahedron, 1994, 50, 305

,0 2 : *- ( >=O CoSANSE CoSANSE = chiral cobalt catalyst Kalra, S.J.S.; Punniyamurthy, T.; Iqbal. J. Tetrahedron Lett., 1994, 35, 4847 -OH

79%

f-BuOOH , ELjNOH , rt [OsOJ , aq. r-BuOH , 12h

HO H OH Beck, C.; Seifert. K. Tetrahedron Lett., 1994, 35, 7221

0.5% Ru complex, 20% Co complex 0.5 O 2 , toluene, 100°C , 36h 2,5-dir-butyl-l ,4-benzoquinone

OH O Wang, G.-Z.; Andreasson,U.; Backvall. J.-E. J. Chem. Soc. Chem. Commun., 1994, 1037

nT T

cat. PdCl2, cat. Adogen 464 9.3h , Na^Oi. °CE, reflux

r^

~ \_/ 0

/ also for primary alcohol —> aldehydes Ai't-Mohand, S.; H6nin, F.; Muzart. J. Tetrahedron Lett., 1995, 36, 2473

O

RuCl3-n H2O , EtOAc -^ 30% MeCO3H

Murahashi. S.-I.: Naota, T.; Oda, Y.; Hirai, N. Synlett, 1995, 733

739?

f-Bu -(

>=O

Section 169

Ketones from Aldehydes

189

,p

N-OH

b OH Co(acac)3,02,MeCN,750C Iwahama, T.; Sakaguchi, S.; Nishiyama, Y.; Ishii. Y. Tetrahedron Lett., 1995, 36, 6923 Bacillus stearothermophilus \kr OH

\

heptane

49% 100% ee (1S,5R) Fantin, G.; Fogagnolo, M.; Giovannini, P.P.; Medici. A.: Pedrini, P.; Poli, S. Tetrahedron Lett., 1995, 36, 441

9H

cat. CoCl2(PPh3)2 , J-BuOOH DCE , heat, 4.5h

93%

pn

aldehydes can also be formed Iver. S.: Varghese, J.P. Synth. Commun., 1995, 25, 2261 )H

e", RuO2 , aq. 4 MeCN, Bu4NOH

Bu^Br Torii, S.; Yoshida, A. Chem. Lett., 1995, 369

Pti

" ^•^

^

89%

Related Methods: Section 48 (Aldehydes from Alcohols and Phenols). SECTION 169: KETONES FROM ALDEHYDES CHO

0.05 Rh(R-BINAP)ClO4 CH2Cl2, rt, 30 min

(3

97) 81% : (>99%ee 3S.4S) Wu, X.-M.; Funakoshi, K.; Sakai. K. Tetrahedron Lett., 1993, 34, 5927

190

Compendium of Organic Synthetic Methods, Vol. 9

Section 169

butanal, CoCl2 CHO

PhCHO leads to the acid

°

71% Punniyamurthy, T.; Kalra, S.J.S.; Iqbal. J. Tetrahedron Lett., 1994, 35, 2959

PhCHO

1. f-BuMe2SiCBr2Li, -78°C -» rt 2. 5gc-BuLi

3. PhCHO Ph^^e^^ Ph 4. HMPA Shinokubo, H.; Oshima. K.: Utimoto. K. Tetrahedron Lett., 1994, 35, 3741 CHO

59%

[Rh(S-BINAP)] C1O4, CH2C12 25°C

59% (78% ee, S) Barnhart, R.W.; Wang, X.; Noheda, P.; Bergens, S.H.; Whelan, J.; Bosnich. B. J. Am. Chem. Soc., 1994, 116, 1821

PhCHO

Me3SiCBr3, CrBr3/LiAlH4 THF , 60°C

Hodgson. P.M.: Comina, P.J. Synlett, 1994, 663 .N

N

N

, EtOH

PhCHO

CH(OEt) 3 ,H + ,THF 70% ^ 2. BuLi, THF, -78°C 94% 3.EtBr 4.H + Katritzkv. A.R.: Lang, H.; Wang, Z.; Zhang, Z.; Song, H. J. Org. Chem., 1995, 60, 7619

PhCHO

, 20% ZnBr2

^

PhCHO ^

THF,3h,25°C Zheng, B.; Srehnik. M. J. Org. Chem., 1995, 60, 3278

II Ph^^

83%

Section 171

Ketones from Amides

SECTION 170:

191

KETONES FROM ALKYLS, METHYLENES AND ARYLS

This section lists examples of the reaction, R-CH2-R' —> R(C=O)-R'. 5% CoSANSE, MeCN cat. 2-oxocyclopentene carboxylate 60°C, 15h , O2 CoSANSE = [bis(salicylidene-N-(methyl-3-hydroxypropionate))] Co Punniyamurthy, T.; Iqbal. J. Tetrahedron Lett., 1994, 35, 4003 Me Me

CH2C12, -78°C -> rt

O Kiselyov, A.S.; Harverv. R.G. Tetrahedron Lett., 1995, 36, 4005

SECTION 171: KETONES FROM AMIDES O Me^ ^JL

T I

OMe I N^

Me

1.2eq.PhLi

^

OMe O Sibi. M.P.: Marvin, M.; Sharma, R. J. Org. Chem., 1995, 60, 5016

P

1.2.2BuLi,-78°C .Ph

2. AcOH 3. K2CO3,65°C

75%

O Bu-

82% Brandange, S.; Holmgren, E.; Leijonmarck, H.; Rodriguez, B. Acta Chem. Scand. B., 1995, 49, 922

/ \ 1.2eq.PhLi (? ( N—C02Et ^Jl 95% * / Ph Prakash, G.K.S.; York, C.; Liao, Q.; Kotian, K.; Olah. G.A. Heteroc\des. 1995, 40, 79

192

Compendium of Organic Synthetic Methods, Vol. 9

Section 172

2eq.EtAlCl 2 ,rt,12h -N

^

'

| -Sty

CH2Cl2,

PIT Kataoka. T.: Iwama, T. Tetrahedron Lett., 1995, 36, 245

PhMgBr

^PI

Kashima. C.: Kita, I.; Takahashi, K.; Hosomi, A. J. Heterocyclic Chem., 1995, 32, 25 REVIEW: "Chemistry of N-Methoxy N-Methyl Amides. Applications in Synthesis. A Review," Sibi. M.P. Org. Prep. Proceed. Int., 1993, 25, 5

SECTION 172: KETONES FROM AMINES 1. "X" 2. H30+ •NHBn H X = octane, 230°C, 2h 40% X = f-BuOK/BuLi/THF/-50°C, 2h 73% Sprules, T.J.; Galpin, J.D.; Macdonald. D. Tetrahedron Lett., 1993, 34, 247

K2Cr2O7 , H2SO4, ether

Etv 75% Et

Et Harris, C.E.; Lee, L.Y.; Dorr, H.; Singaram. B. Tetrahedron Lett., 1995, 36, 2921

Section 174

Ketones from Ethers

OH

193

TS-1, H2O2, acetone '

*

:0

reflux, 4h \ / TS-1 = zeolite titanium silicalite Joseph, R.; Sudalai, A.; Ravindranathan. T. Tetrahedron Lett., 1994, 35, 5493

\ Gagnon, J.L.; Zaiac Jr.. W.W. Tetrahedron Lett., 1995, 36, 1803

75%

86%

O

SECTION 173: KETONES FROM ESTERS O

'C°2Et

1.2.1eq.SmI2

2.H 0 +

Ph

74%

3

Molander. G.A.: McKie, J.A. J. Org. Chem., 1993, 58, 7216

O

k

1. 2.MeI,LiBr(-C0 2 ) 3.H +

^ O Shibata. I.: Nishio, M.; Baba, A.; Matsuda, H. Chem. Lett., 1993, 1953

SECTION 174:

70%

KETONES FROM ETHERS, EPOXIDES AND THIOETHERS

ph

SiOyhexane/CH2Cl2 O rt,ld Rao, T.B.: Rao. J.M. Svnth. Commun., 1993, 23, 1527 .OTBDMS

, aq. MeCN , hv

9, w

^

.

1,4-dicyanonaphthalene ^^^ Ph Pandey. G.: Sochanchingwung, R. /. Chem. Soc. Chem. Commun., 1994, 1945

194

Compendium of Organic Synthetic Methods, Vol. 9

Section 174

e-,MeCN-H 2 O LiNO3 54% Shono. T.: Yamamoto, Y.; Takigawa, K.; Maekawa, H.; Ishifune, M.; Kashimura. S. Chem. Lett., 1994, 1045

5% Pd(OAc)2,15% PPh3 PhH, reflux can also generate aldehydes Kulasegaram, S.; Kulawiec. R.J. J. Org. Chem., 1994, 59, 7195 ,Bu O

/

v

Bu

/

^

BU

\

/

O

\

f

CHO

MABR, CH2C12, -20°C (0 : 100) 73% SbF3, PhH, 25°C (85 = 15) 62% Maruoka, K.; Murase, N.; Bureau, R.; Ooi, T.; Yamamoto. H. Tetrahedron, 1994, 50, 3663 H BusSnH , AIBN, PhH reflux, 18h

AX

Ptt

+

Ph

O

50% Crich. P.: Yao, Q. J. Chem. Soc. Chem. Commun., 1993, 1265

C7H15

32%

Me4FeLi2, ether,-78°C

C7Hi5

45 min

^—O

„. 81%

Kaufftnann. T.: Neiteler, C.; Neiteler, G. Chem. Ber., 1994,127, 659 Bz

O

BF3-OEt2 , CH2C12 , 0°C

I

\

^

OBz

Fujioka, H.; Kitagaki, S.; Imai, R.; Kondo, M.; Okamoto, S.; Yoshida, Y.; Akai, S.; Kite. Y. Tetrahedron Lett., 1995, 36, 3219

Section 175

Ketones from Halides

SECTION 175:

195

KETONES FROM HALIDES AND SULFONATES l.f-BuLi,THF,-78°C

H

-78°C -> rt Selnick. H.G.: Bourgeois, M.L.; Butcher, J.W.; Radzilowski, E.M. Tetrahedron Lett., 1993, 34, 2043 PhB(OH)2 , CO , 80°C , 5h 3% PdCl2(MeCN)2 ^ \

it

ff

N02

y

*•

3 eq. K2C03, anisole

(v

ph/

^

Ishiyama, T.; Kizaki, H.; Miyaura, N.; Suzuki, A. Tetrahedron Lett., 1993, 34, 7595 1. Zn/Ag-graphite, THF , 25°C //

2. benzoyl chloride

xx

7/

Fiirstner. A.: Singer, R.; Knochel. P. Tetrahedron Lett., 1994, 35, 1047 ] Jr

1. Riecke zinc, THF, reflux, 2.5h *• 2. PhCOCl, CuCN, LiBr ,.

Ns/ ?h T 95% JL

Hanson, M.V.; Brown, J.D.; Rieke. R.D.: Niu, QJ. Tetrahedron Lett., 1994, 35, 7205 /°Me (OC)5M=^ \ ph

1. MeLi, LiBr , C1CH2I, -78°C -> 20°C 2. H20 , 20°C

° _J1 Me^\ p

M = Mo = Cr Barluenga. J.: Bernad Jr., P.L.; Concell6n, J.M. Tetrahedron Lett., 1994, 35, 9471

l.Zn,THF,40°C 2.CoBr 2 ,CO,THF,NMP "" ^ 25°C, 8h Devasagayaraj, A.; Knochel. P. Tetrahedron Lett., 1995, 36, 8411

II

^

59%

196

Compendium of Organic Synthetic Methods, Vol. 9

I

Section 176

, 5 atm CO

PdCl2/PPh3 , NEt 3 , PhH 120°C, 20h Satoh, T.; Itaya, T.; Okuro, K.; Miura. M.: Nomura, M. J. Org. Chem., 1995, 60, 7267 >Bn

xOEt

OBn , BuLi

OTBDMS THF ,-78°C *OTf

2.aq.HF,MeCN

88x99% Hosoya, T.; Hasegawa, T.; Kuriyama, Y.; Matsumoto, T.: Suzuki. K. Svnlett. 1995, 111

2 eq. DMSO, microwave

u • L U

Br Villemin. P.: Hammadi, M. Synth. Comtnun., 1995, 25, 3145 Related Methods:

O

75%

Section 177 (Ketones from Ketones). Section 55 (Aldehydes from Halides).

SECTION 176: KETONES FROM HYDRIDES This section lists examples of the replacement of hydrogen by ketonic groups, R-H -» R(C=O)-R'. For the oxidation of methylenes, R2CH2 -> R2C=O, see section 170 (Ketones from Alkyls).

O

l%RuCl 2 (PPh 3 ) 3 ,PhH r-BuOOH, 1

0

%a

q

S^jP . Na2SO3 I

S^^/

41% conversion I I

I

47% 7% Murahashi. S.: Oda, Y.; Naota, T.; Kuwabara, T. Tetrahedron Lett., 1993, 34, 1299 Cr02Cl2,CCl4

PIT ^Ph

ultrasound

Luzzio. F.A.: Moore, W.J. / Org. Chem., 1993, 58, 512

Ph

Ph

Section 176

Ketones from Hydrides

197

BaRu(O)2(OH)3, LiCl, CH£12

69%

AcOH , 23°C, Ih Lau. T.-C.: Mak, C.-K. J. Chem. Soc. Chem. Commun., 1993, 766

, CH2Cl2

-20°C, 3h

O 98% Banwell. M.G.: Haddad, N.; Huglin, J.A.; MacKay, M.F.; Reum, M.E.; Ryan, J.H.; Turner, K.A. J. Chem. Soc. Chem. Commun., 1993, 954

OMe

0.2 Yb(OTf)3 , MeN02 ,_ -2 Ac20,18h

, , _ „, , >-(\ /) - OMe

Kawada. A.: Mitamura, S.; Kobavashi. S. J. Chem. Soc. Chem. Commun., 1993, 1157 Ac£>,0.2Sc(OTf) 3

*-

OMe

(v

>

/)

OMe

MeNO2, 50°C , 4h Kawada. A.: Mitamura, S.; Kobavashi. S. Svnlett. 1994, 545

O

10% N-hydroxyphthalimide

||

73% Ph'— \ Ishii. Y.: Nakayama, K.; Takeno, M.; Sakaguchi, S.; Iwahama, T.; Nishiyama, Y. J. Org. Chem., 1995, 60, 3934 PhCN, O2,100°C , 20h

f

MeO

(x

>

Hf(OTf)4, Ac2O , LiClO4—MeNO2

^

-

MeO

Hachiya, I.; Moriwaki, M.; Kohayashi. S. Tetrahedron Lett., 1995, 36,409

198

Compendium of Organic Synthetic Methods, Vol. 9

Section 177

PhCOCl, toluene, reflux 0.1 [ReBr(CO)5]

91% (11:4:85 o:m:p) Kusama, H.; Narasaka. K. Bull. Chem. Soc. Jpn., 1995, 68, 2379

SECTION 177: KETONES FROM KETONES This section contains alkylations of ketones and protected ketones, ketone transpositions and annulations, ring expansions and ring openings and dimerizations. Conjugate reductions and Michael alkylations of enone are listed in Section 74 (Alkyls from Alkenes). For the preparation of enamines or imines from ketones, see Section 356 (Amine-Alkene). 1. CF3SO3SiMe3 , MeCN Me3Si-S-SiMe3 , rt -^> 2. aq. NaHCO3

S 76%

Degl'Innocenti. A.: Capperucci. A.; Mordini, A.; Reginato, G.; Ricci, A.; Cerreta, F. Tetrahedron Lett., 1993, 34, 873

0

Pt

JL ^

l. PhCN,TiCl4-Zn

O II

Ph

Ph

2. 3% HC1

Ph 86% 7% Gao, ].; Hu, M-Y.; Chen, J-x.; Yuan, S.; Chen, W-x Tetrahedron Lett., 1993, 34, 1617

SMe

^>

IS

^~~^

OMe

SnCl 4 , u

N.

OMe

Me

86%

Patra, P.K.; Patro, B.; Ila. H.: Junjappa. H. Tetrahedron Lett., 1993, 34, 3951

Section 177

Ketones from Ketones

199

•»'Si(iPr)3

92%

-78°C -» -20°C (5:1 anti:syri) Knolker. H.-J.: Graf, R. Tetrahedron Lett., 1993, 34, 4765 1. LDA, THF, TBDMSC1 O

2. hv , DCN , aq. MeCN Pyrex filter Me( 98x72% Pandev. G.: Krishna, A.; Girija, K.; Karthikeyan, M. Tetrahedron Lett., 1993, 34, 6631 l.LiN(TMS)2 2. MnBr2 3. Mel, 22°C , 4h 95%

Reetz. M.T.: Haning, H. Tetrahedron Lett., 1993, 34, 7395

hv, LiClO4 3h, NEt3

Cossv. J.: Furet, N. Tetrahedron Lett., 1993, 34, 8107 l.KH,ether, 3h 2. BuBr, ether, it, 18h

JJ^

Bu

42%

+ 56% cyclohexanone

/ Bates. R.B.: Taylor, S.R. J. Org. Chem., 1993, 58, 4469 1. PhMeN-MnMe , 20°C THF/DMSO r

ft C3HXssXXxC3

2. Mel

I

93%

Cahiez. G.: Figadere, B.; C16ry, P. Tetrahedron Lett., 1994, 35, 3065

Me

200

Compendium of Organic Synthetic Methods, Vol. 9

Section 177

TMS

CF3CO2Ag, Mel CH2C12, -78°C -> rt

(6.1 Angers, P.; Canonne. P. Tetrahedron Lett., 1994, 35, 367

1)

:

78%

Bu 3 SnH, AIBN

PhS

X

1J

Chen, L.; Gill, G.B.; Pattenden. G. Tetrahedron Lett., 1994, 35, 2593 'SiMe3

l.MeLi 2. MnCl2 3. PhCH2Br

Cahiez. G.: Chau, K.; C16ry, P. Tetrahedron Lett., 1994, 35, 3069 O

MeCHN2 , Me3Al ,0°C

°

.___IL ,, Bu^^\ ---- s.n

55%

CH 2 Cl 2 ,lh

Me Maruoka, K.; Concepcion, A.B.; Yamamoto. H. J. Org. Chent, 1994, 59, 4725

l _y / *-c,

2.5 eq. Bu 3 SnH, AIBN 8h slow addition

fS^Y^ I

I

k/-1IT^

0

Dowd. P.: Zhang, W.; Mahmood, K. Tetrahedron Lett., 1994, 35, 5563

57% O

Section 177

Ketones from Ketones

201

OH

SC-1 , Ni2B , H2 (1 atm)

(>99 : Belisle, C.M.; Young, Y.M.; Singaram. B. Tetrahedron Lett., 1994, 35, 5595 ^ Ph.

.Ph

1) >99%

/

Ph.\^-CHPh rup. 2

I O

Yb , THF , 40°C , 2h *

Ph.

.Ph

{I

68% 29% Taniguchi. Y.: Nagafuji, A.; Makioka, Y.; Takaki. K.: Fuiiwara. Y. Tetrahedron Lett., 1994, 35, 6897

hv , NEt3

N

48%

Kirschberg, T.; Mattav. J. Tetrahedron Lett., 1994, 35, 7217 Rh2(O2CR*)4, CH£12, -20°C , 2h

64% (77% ee, S) Watanabe, N.; Ohtake, Y.; Hashimoto. S.: Shiro, M.; Ikegami, S. Tetrahedron Lett., 1995, 36, 1491

84%

S cat. TMSOTf, rt, CH2C12, 5h Ravindranathan. T.: Thavan. S.P.: Awachat, M.M.; Kelkar, S.V. Tetrahedron Lett., 1995, 36, 2277

202

Compendium of Organic Synthetic Methods, Vol. 9

Section 179

CH2I2, SmI2, THF, 5h

61%

Fukuzawa. S.: Tsuchimoto, T. Tetrahedron Lett., 1995, 36, 5937 - NaBH3CN, AIBN PIT

—

'-BuOH.heat 86%

Giovannini, R.; Petrini. M. Svnlett. 1995, 973 REVIEW:

"Organotin Enolates in Organic Synthesis. A Review," Shibata. L: Baba, A. Org. Prep. Proceed. Int., 1994, 26, 123 Related Methods: Section 49 (Aldehydes from Aldehydes). SECTION 178: KETONES FROM NITRILES NO ADDITIONAL EXAMPLES

SECTION 179: KETONES FROM ALKENES 1,4-dimethoxybenzene (sensitizer)

».

N^ / ph/

hv , MeCN, 12h , rt Pti ~,,—,» pl{ Bhalerao. U.T.: Sridhar, M. Tetrahedron Lett., 1993, 34, 4341

II li

\ k

^ V^i

O

90%

conversion (quant.)

TlOAc, CO, MeCN 80°C,16h

+

10% [Pd(OAc)2/2 PPh3] 75% Grigg. R.: Khalil, H.; Levett, P.; Virica, J.; Sridharan, V. Tetrahedron Lett., 1994, 35, 3197

Section 179

Ketones from Alkenes

203

10% Pd(OAc)2 , 20% PPh3 Et4NCl , CO

•o Grigg. R.: Redpath, J.; Sridharan, V.', Wilson, D. Tetrahedron Lett., 1994, 35, 4429

O

l . Et2BH-SMe2 , ether , 25°C 2. Et2Zn , neat , 0°C

Q f] JL

.^

-*" 3. CuCN-2 LiCl LiQ,, THF THF,, 0°C 0°C | A D^rrvi I 4. PhCOCl

r | J

IT

Langer, F.; Devasagayaraj, A.; Chavant, P.-Y.; Knochel. P. Svnlett. 1994, 410 Me3SiN3,CH2Cl2,CrO3

-

^4>

Q

59%

Reddy, M.V.R.; Kumareswaran, R.; Vankar. Y.D. Tetrahedron Lett., 1995, 36, 6751 1. [CoCl2-THF/PhEt2N:BH3, PhH, CO] 2. CO, 6h 3.25°C,36h 4. H2O2, NaOH , NaOr-Bu 70%

Rao, M.L.N.; Periasamv. M. Tetrahedron Lett., 1995, 36, 9069

, Ni(cod)2 2PPh 3 ,DCE

o

T o

(>20 1) 99% : Lautens. M.: Edwards, L.G.; Tarn, W.; Lough, AJ. J. Am. Chem. Soc., 1995, 117, 10276

204

Compendium of Organic Synthetic Methods, Vol. 9

Section 180

. C12C=C=0 2. BuaSnH, AIBN /

85% (84:16) Dowd. P.: Zhang, W.; Geib, SJ. Tetrahedron, 1995, 51, 3435 See also:

Section 134 (Ethers from Alkenes). Section 174 (Ketones from Ethers).

SECTION 180:

KETONES FROM MISCELLANEOUS COMPOUNDS

Conjugate reductions and reductive alkylations of enones are listed in Section 74 (Alkyls from Alkenes). , TFP , CH2C12

:N-NHPh

*•

>=O

20°C , 30 min

f

92%

TFP = 1,1,1-trifluoropropane Altamura, A.; Curci. R.: Edwards, J.O. J. Org. Chem., 1993, 58, 7289

acetone, NOH

0°C, 10 min

^

(

>=O \ 80%

Olah. G.A.: Liao, Q.; Lee, C.-S.; Prakash. G.K.S. Synlett, 1993, 427 Ph

O 3 , CH2C12, -2°C, 2h

y»^N-OH *PIT Yang. Y.: Li, T.; Li, Y. Synth. Commun., 1993, 23, 1121

Ph

// ?

N—NHTs

Ph /=° PIT

95%

PhI(OAc)2, MeCN, rt, 10 min *-

Ph

O // f

Me

Me 87%

Zeng, H.; Chen. Z.-C. Synth. Commun., 1993, 23, 2497

Section 180

Ketones from Misc.

-NHTs

205

TS-1, H2O2, MeOH , 4h

TS-1 = titanium silicate molecular sieves Kumar, P.; Hegde, V.R.; Pandey, B.; Ravindranathan. T. 7. Chem. Soc. Chem. Commun., 1993, 1553 Ph

KMnO4, aq. MeCN, rt, Ih

Ph

\=N-OH

-

/==O

95%

Wali, A.; Ganeshpure, P.A.; Satish. S.Bull. Chem. Soc. Jpn., 1993, 66, 1847 N 2

°

NaBHVH202 K 2 CO 3 ,MeOH

1^

73%

J

Ballini. R.: Bosica, G. Synthesis, 1994, 723 NNHCONH2

phi(OAc)2,aq.MeCN

Chen, D.W.; Chen. Z.C. Synthesis. 1994, 111 / < \

\ >=N-NMe2 /

(BU4N)2S208, DCE

-

{

)=0

90%

reflux, Ih

Choi, H.C.; Kim. Y.H. Svnth. Commun., 1994, 24, 2307

Ph

f

N-OH

Bentonite/Ag2CO3, PhH

^

/f

Ph—^

50%

\, reflux, 4h \, Me Me Sanabria, R.; Miranda. R.: Lara, V.; Delgado, F. Synth. Commun., 1994, 24, 2805

(Bu4N)2S2O8 , DCE , reflux N-NHTs

Ih

/==O

95%

Chen. F.: Yang, J.; Zhang, H.; Guan, C.; Wan, J. Synth. Commun., 1995, 25, 3163 REVIEW: "Macrocycle Synthesis: Cyclic Ketones, Ketoalkenes, Diketones and Dienes of Ring Size C2i to C26," Forbes. M.D.E.: Dang, Y. Org. Prep. Proceed. Int., 1993, 25, 309

206

Compendium of Organic Synthetic Methods, Vol. 9

Section 180A

SECTION 180A: PROTECTION OF KETONES / \ [Rh(MeCN)3(triphos>] (OTf)2 0 , 0 ^ a/v»trm*» rt rt ,4h Ah >?\ acetone, Ptf Me Ma, S.; Venanzi. L.M. Tetrahedron Lett., 1993, 34, 8071 HS

^\

P H DV.—*"**^^»_ Ph-*"^^, Me

SH

\-j •™*

O°

rA/ "i

-*

LAJ s92%

Zhang. Y.: Yu, Y.; Lin, R. Org. Prep. Proceed. Int., 1993, 25, 365

/7-TsOH , PhH , reflux , cat. TMSI ^^

DDQ, H 2 O, CH2C12

/

95% McDonald. C.E.: Nice, L.E.; Kennedy, K.E. Tetrahedron Lett., 1994, 35, 57 Me3Si OSiMe3

^Wo \ / '

'

CF3S03SiMe<3, CH2C12 ' °

LiBF4, MeCN, heat 96% Lillie, B.M.; Avery, M.A. Tetrahedron Lett., 1994, 35, 969 /

\\

\ /OEt

X /\Et

AcCl, 2% SmCl3, rt 15min

/

( \

\

// ==0 95%

Wu. S.-H.: Ding, Z.B. Synth. Commun., 1994, 24, 2173

Section 180A

/ ( \

\ k

Protection of Ketones

207

cat. Pd(OAc)2,2 NaOAc, O2 OSiMe3 ff

*DMSO

/ ( \

\ )= /

Larock. R.C.: Hightower, T.R.; Kraus, G.A.; Hahn, P.; Zheng, D. Tetrahedron Lett., 1995, 36, 2423 /

s\

SeO2, AcOH, rt, 25 min

"X

Ph ^^ aldehydes can also be used Haroutounian. S.A. Synthesis, 1995, 39

"

CuSO4/SiO2,CHCl3 20°C, 2d

Caballero, G.M.; Gros. E.G. Svnth. Commun., 1995, 25, 395

O

HO

OH'™ 2 0 2

»- r-Bu

cat. TMSOTf, iPrOTMS -20°C, 3h Kurihara, M.; Miyata, N. Chem. Lett., 1995, 263 See Section 362 (Ester-Alkene) for the formation of enol esters and Section 367 (Ether-Alkenes) for the formation of enol ethers. Many of the methods in Section 60A (Protection of Aldehydes) are also applicable to ketones.

208

Compendium of Organic Synthetic Methods, Vol. 9

Section 185

CHAPTER 13 PREPARATION OF NITRILES

SECTION 181: NITRILES FROM ALKYNES NO ADDITIONAL EXAMPLES SECTION 182: NITRILES FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES SECTION 183: NITRILES FROM ALCOHOLS AND THIOLS Me2C(CN)OH , MeCN , DEAD Wilk. B.K. Synth. Commun., 1993, 23, 2481 SECTION 184: NITRILES FROM ALDEHYDES 1. Me2NNH2 , MeOH , rt 2. "crude",MeOH,0°C 2.4 MMPP-6 H2O MMPP = magnesium monoperoxyphthalate Fernandez, R.; Gasch, C.; Lassalwtta. J-M.: Llera, J-M.; Vazquez, J. Tetrahedron Lett., 1993, 34, 141 SECTION 185:

NITRILES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES

Section 190

Nitrites from Halides

209

SECTION 186: NITRILES FROM AMIDES 2PPh 3 ,2CCl 4

97%

3NEt 3

CN

other reagents are also given that lead to this conversion Walters. M.A.: Hoem, A.B.; Arcand, H.R.; Hegeman, A.D.; McDonough, C.S. Tetrahedron Lett., 1993, 34, 1453 Ag2O , EtI, PhH , 25°C +•

Ph

CN

82%

(dark), MS 4A, 12h Sznaidman, M.L.; Crasto, C.; Hecht. S.M. Tetrahedron Lett., 1993, 34, 1581 NaOCl, NaBr, PhH/H2O

•"

TBAHSO4 , Na3PO4-12 H^O Correia. J. Synthesis. 1994, 1127

^\

Bu

C=N

55%

SECTION 187: NITRILES FROM AMINES NO ADDITIONAL EXAMPLES SECTION 188: NITRILES FROM ESTERS Me3SiCN, Pd(PPh3)4 'OAc

THF, reflux , 16h 98% (E:Z, >9:1)

Tsuji. Y.: Yamada, N.; Tanaka, S. J. Org. Chem., 1993, 58, 16 SECTION 189:

NITRILES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDITIONAL EXAMPLES

SECTION 190: NITRILES FROM HALIDES AND SULFONATES l.BuLi,THF,-100°C 2. ZnI2, -100°C -> 0°C -I

-

<

)

CN

3. TosCN, -78°C -> rt, 3h 84% Klement, I.; Lennick, K.; Tucker, C.E.; Knochel. P. Tetrahedron Lett., 1993, 34, 4623

210

Compendium of Organic Synthetic Methods, Vol. 9

Section 194

Me2C(CN)OH , MeCN, TMG TMG = 1,1,3,3-tetramethylguanidine Dowd. P.: Wilk, B.K.; Wlostowski, M. Synth. Commun., 1993, 23, 2323 TiCLj , TMSCN , CH2C12 , 0°C -^

Ph^CHCl

Ph^CH—CN

93%

Zieger. H.E.: Wo, S. J. Org. Chem., 1994, 59, 3838

SECTION 191: NITRILES FROM HYDRIDES NO ADDITIONAL EXAMPLES

SECTION 192: NITRILES FROM KETONES i , / —\

f-Bu

Q

4

- NaOMe

also works with aldehyde substrates Santiago, B.; Mevers. A.I. Tetrahedron Lett., 1993, 34, 5839 l.Me(Cl)A!NH2 Cp3

2. f-BuOK

Kende. A.S.: Liu, K. Tetrahedron Lett., 1995, 36, 4035 SECTION 193: NITRILES FROM NITRILES Conjugate reductions and Michael alkylations of alkene nitriles are found in Section 74D (Alkyls from Alkenes). NO ADDITIONAL EXAMPLES

SECTION 194: NITRILES FROM ALKENES NO ADDITIONAL EXAMPLES

Ph—CN

Section 195

SECTION 195:

Nitriles from Misc.

211

NITRILES FROM MISCELLANEOUS COMPOUNDS

83% Dandgar. B.P.: Jagtap, S.R.; Ghodeshwar, S.B.; Wadgaonkar, P.P. Synth. Commun., 1995, 25, 2993

212

Compendium of Organic Synthetic Methods, Vol. 9

Section 196

CHAPTER 14 PREPARATION OF ALKENES

SECTION 196: ALKENES FROM ALKYNES Ph

Ph-CsC-Ph , DMF, 120°C 10% Pd(OAc)2 , 20% PPh3 2 TlOAc, 36h

I

^^ ^

45%

Grigg. R.: Kennewell, P.; Teasdale, A.; Sridharan, V. Tetrahedron Lett., 1993, 34, 153 OTs -

(PhMe2Si)2CuCNLi2 THF, -78°C -» rt

Reming. I.: de Marigorta, E.M. Tetrahedron Lett., 1993, 34, 1201

C3H7 Cp2Zi(CH2=CH2). Id £OaL

2.H + Takahashi. T.: Kondakov, D.Y.; Suzuki, N. Tetrahedron Lett., 1993, 34, 6571

^J

.N-OBn

BnO-: OsSiH, hv (sunlamp) 2h, hexane 70%

Pattenden. G.: Schulz, DJ. Tetrahedron Lett., 1993, 34, 6787

Section 196

Alkenes from Alkynes

O

NO2

213

10% Pd(OAc)2 20% PPh3 , DMF Tl(OAc), 130°C 18h

60%

'C02Et Et02C' \X>2Et Brown, S.; Clarkson, S.; Grigg. R.: Sridharan, V. Tetrahedron Lett., 1993, 34, 157

. Cp2Zr(H)Cl , 20°C , 20 min 2.5%AgCl 4 10 min

O

Wipf. P.: Xu, W. J. Org. Chem., 1993, 58, 825

/

92%

TBDMSC

l.r-BuLi,pentane/ether 2. -78°C -^ rt -^ -78°C

^^_ ^

p_

3.D.O Bailev. W.F.: Ovaska, T.V. J. Am. Chem. Soc., 1993, 115, 3080 f-Bu. ^

1. PhSCu, ether, BuLi, -35°C

,_Bu

2. add alkyne via syringe pump OAc Nantz. M.H.: Bender, D.M.; Janaki, S. Synthesis, 1993, 577

/ (CH2)3

1. r-B uLi, pentane/ether, -78°C 2. +20°C, Ih 3. MeOH

<, J Bailey. W.F.: Ovaska, T.V. Chem. Lett., 1993, 819

85%

214

Compendium of Organic Synthetic Methods, Vol. 9

Section 196

!.CH2=CH2,Cp2ZrBu2 Et = Et ^^ 2.H + Takahashi. T.: Xi, Z.; Rousset, C.J.; Suzuki, N. Chem. Lett., 1993, 1001 _ Ph-^=- Et

HCO2H, NEt 3 , 3h

Et

Ph

^

Et

\

/

^=/

cat. Pd2(dba)3-PBu3

89% cis + 5% trans Tani, K.; Ono, N.; Okamoto, S.; Sato. F. J. Chem. Soc. Chem. Commun., 1993, 386 'SiMe3

CO, EtOH , PdCl2(PP3)2, PhH Me3Si 5SnCl2,90°C,1.5h

•-* n i«-ii

77%

Takeuchi. R.: Sugiura, M. J. Chem. Soc., Perkin Trans. 1., 1993, 1031

Bu

1. 3 eq AlMe3 ,0.2 Cp2ZrCl2 1.5 eq. H 2 O, CU£\2, -70°C ^^^^^

Bu

B

\ ^

\

— I. .—

*4*"

2. 3M HC1

/ (97 Wipf. P.: Lim, S. Angew. Chem. Int. Ed. Engl., 1993, 32, 1068

:

3) quant.

PhjSiH , BEt3 , PhH

42% (12:1 Z:£) Miura, K.; Oshima. K.: Utimoto. K. Bull. Chem. Soc. Jpn., 1993, 66, 2356 ^__

<~v

SiO2 — O-Si-H C

3»7T

C-H-7 ^^-C3H 7

^ / C Pd(PPh3)4, AcOH, 16h 3H7 Kini, A.D.; Nadkami, D.V.; Frv. J.L. Tetrahedron Lett., 1994, 35, 1507

\

- -

97%

CrCl2, cat. NiCl2 DMF,25°C,18h Hodgson. D.M.: Wells, C. Tetrahedron Lett., 1994, 35, 1601

||

|

|

52%

Section 196

Alkenes from Alkynes

215

l.Cp£r(H)Cl,THF,rt PhS(H2C)3x

2.H20

Lipshnt7. B.H.: Lindsley, C.; Bhandari, A. Tetrahedron Lett., 1994, 35, 4669 0

O

.^\ >C°2Me

C02Me

Me

0

5%CPCo(CO)2 1 PhH, reflux, hv

\

^\ yC°2Me

/

\

(77

:

/

23) 69%

54% de

Cruciani, P.; Aubert, C.; Malacria. M. Tetrahedron Lett., 1994, 35, 6677

H

SPh

A, ether 2. 2 eq. BuLi, -40°C , Me2S — 3. NH3/NH4C1

+-

Bu Bu \ / ^=^

61%

(> 99% 2) Creton, I.; Marek. I.: Brasseur, D.; Jestin, J.-L.; Normant. J.-F. Tetrahedron Lett., 1994, 35, 6877

CC^Me

hv, 1% CpCo(CO)2, PhH, heat

93%

Stammler, R.; Malacria. M. Synlett, 1994, 92 ,SiMe3

LCp 2 ZrBu 2 ,PMe 3

EtO 7 % 3 HO* * (53:47 cis:trans) Takahashi. T.: Kondakov, D.Y.; Suzuki, N. Chem. Lett., 1994, 259

J==\ / \X 92% Ph Sakai. M.-. Takai, Y.; Mochizuki, H.; Sasaki, K.; Sakakibara, Y. Bull. Chem. Soc. Jpn., 1994, 67, 1984 Ph

^=

NiBr2-Zn, diphos, H2

^

216

Compendium of Organic Synthetic Methods, Vol. 9

Section 197

VSiEt3

OSiEt, 3% (PCy3)2Cl2Ru=CHCH=CPh2 CH2C12 , (0.6 M), 25-C , 8h

Me Me 95% Kim, S.-H.; Bowden, N.: Grubbs. R.H. J. Am. Chem. Soc., 1994, 116, 10801

MeaSil, Me2Zn, dioxane

Pn

x.

61% *\^^ • SiMe3 5% Pd(PPh3)4,25°C, 8 h | Chatani, N.; Amishiro, N.; Morii, T.; Yamashita, T.: Murai. S. J. Org. Chem., 1995, 60, 1834

Ph

==

20% Cp2Ti(PMe3)2, HSi(OEt)3 -Me

Crowe. W.E.: Rachita, M.J. J. Am. Chem. Soc., 1995, 117, 6787 Br V

SmI 2 ,THF,DMPU

^Ph

Ph-

Zhou, Z.; Larouche, D.; Bennett. S.M. Tetrahedron, 1995, 51, 11623 SECTION 197: ALKENES FROM ACID DERIVATIVES 0.01 PdCl2(PPh3)2, PPh3 C 2H

° 250°C, N2 Miller. J.A.: Nelson, J.A.; Byrne, M.P. J. Org. Chem., 1993, 58, 18

, Me3Si-SiMe3, toluene Ph^

^ Cl

5% Pd(dba)2, 80°C, 4h

SiMe3 Ph" 1

Obora, Y.; Tsuii. Y.: Kawamura, T. / Am. Chem. Soc., 1995, 117, 9814

86%

Section 199

Alkenes from Aldehydes

217

SECTION 198: ALKENES FROM ALCOHOLS AND THIOLS H-montmorillonite » dioxane (air free) reflux, 6h (81 : 19) 91% Kantam. ML.: Santhi, P.L.; Siddiqui, M.F. Tetrahedron Lett., 1993, 34, 1185 OH PIT

1. SOC12, NEt 3 ,0°C

JL ^v^ .NMe(OMe) 2.DBU,0°C -> ^Y^ ^p

OH rt II ^^^ NMe(OMe) Ph^ ^^ ^|^

Ji OH 0 (96-98% ee) Bennani, Y.L.; Sharpless. K.B. Tetrahedron Lett., 1993, 34, 2083

CioH23 N

/ Mo(acac)3, dioxane, reflux CioH23 s ^-OH ^=\

(1 : Kantam. M.L.: Prasad, A.D.; Santhi, P.L. Synth. Commun., 1993, 23, 45

Jl O

92%

CioH23

^

/ \

1) 92%

73% Dorta, R.L.; Suarez. E.: Betancor, C. Tetrahedron Lett., 1994, 35, 5035

SECTION 199: ALKENES FROM ALDEHYDES H

Me

C02Me

1-2LDA 2. PhCHO

P

78% / ^ (>98:2 , E:Z) Coutrot. Ph.: Orison, C.; Gdrardin-Charbonnier, C.; Lecouvery, M. Tetrahedron Lett., 1993, 34, 2767

218

Compendium of Organic Synthetic Methods, Vol. 9

Section 199

Me2CH2PPh3+ Br' BuLi, THF, -78°C

HO Ph

[94:6£:Z(>98%ee,R)] Bhushan, V.; Lohray, B.B.: Enders. D. Tetrahedron Lett., 1993, 34, 5067 l.H 2 S,THF,-30°C »

XTTT X T T T

O

CH

.On0/"1

4h

*

CHO

4.MgSO4,-30°C 5. CaC03, Pb(OAc)4 ^=/ 6. THF, reflux 7. PPh3 , THF, reflux Collazo, L.R.; Guziec Jr.. F.S. J. Org. Chem., 1993, 58, 43 'Ac

80x93%

CyH 15CHO, Zn , CrCl3 , PMF/THF C7H15"

Bf

56% (91:9 E:Z)

Knecht, M.; Boland. W. Svnlett. 1993, 837 /CN

CH2(CN)2, CdI2, neat PhCHO

^

J={ / \ Ph CN Prajapati, P.; Sandhu. J.S. J. Chem. Soc., Perkin Trans. 1., 1993, 739

95%

heaat, 5 min

Bu£nCH2Br2 , 25°C Li, CrCl2 , DMF/THF

61% Hodgson. D.M.: Boulton, L.T.; Maw, G.N. Tetrahedron Lett., 1994, 35, 2231

HO

[PPh3=CHMe/I2/ 2 NaNTMS2]

i

i

(10:1 Z:E) Chen, J.; Wang, T.; Zhao. K. Tetrahedron Lett., 1994, 35, 2827 (Me3Si)2CBr2,CrCl2 PhCHO PMF,25°C

/-<._... SiMe

„.. Ph Hodgson. P.M.: Comina, PJ. Tetrahedron Lett., 1994, 35, 9469

3

I

42%

Section 200

Alkenes from Alkyls

Et02C

219

—PPh3+ Br ,dioxane

C6H13CHO , hv, K2CO3 , H 2 0,90°C, 2h

70% (78:22 E:Z) (without hv 12:18 E:Z)

Matikainen, J.K.; Kaltia, S.; Hase. T. Svnlett. 1994, 817 PhCHO, DMSO ^^""^s^^^

*"

FtOif

cat.CsF,rt-» 100°C Bellassoued. M.: Ozanne, N. / Org. Chem., 1995, 60, 6582 Me3Si PhCHO Petasis. N.A.: Staszewski, J.P.; Fuk, D.-K. Tetrahedron Lett., 1995, 36, 3619

;

Z

°2Et 1. KHMDS , THF, Ih A 5 eq. 18-crown-5, -78°C / ^ \ 2. PhCHO \

E

^^

pho/X— (99 Ando. K. Tetrahedron Lett., 1995, 36, 4107 .CHO

Me3SiCH=C=O , BF3-OEt2

yCO2H PI

90% (1:1 E:Z) Black. T.H.: Zhang, Y.; Huang, J.; Smith, D.C.; Yates, B.E. Synth. Commun., 1995, 25, 15

Related Methods: Section 207 (Alkenes from Ketones).

SECTION 200:

ALKENES FROM ALKYLS, METHYLENES AND ARYLS

Tbis section contains dehydrogenations to form alkenes and unsaturated ketones, esters and amides. It also includes the conversion of aromatic rings to alkenes. Reduction of aryls to dienes is found in Section 377 (Alkene-Alkene). Hydrogenation of aryls to alkanes and dehydrogenations to form aryls are included in Section 74 (Alkyls from Alkenes).

220

Compendium of Organic Synthetic Methods, Vol. 9

Section 203

CgK.THF ^

II

II

I

42%

Weitz, I.S.; Rahinovitz. M. J. Chem. Soc., Perkin Trans. L, 1993, 117 Br Mi

OHC-

' \

* //

~"

Pseudomonas cepacia AC1100 \

CO2H

"OMe Artaud, I.; Tomasi, I.; Martin, G.; Petre, D.; Mansuy, D. Tetrahedron Lett., 1995, 36, 869

SECTION 201: ALKENES FROM AMIDES Related Methods:

Section 65 (Alkyls from Alkyls). Section 74 (Alkyls from Alkenes). PhLi , THF , 0°C

'hr^^vT*^ NMe2 ~2 |^\ - L /

,0°C,13h

Jurata, H.; Ekinaka, T.; Kawase, T.; Oda. M. Tetrahedron Lett., 1993, 34, 3445 SECTION 202: ALKENES FROM AMINES CH2=CH2 , BuONO AcOH , 0.05 Pd(OAc)2 Seller. M.: Fischer. H.; Kuhlein, K. Tetrahedron Lett., 1994, 35, 8773 SECTION 203: ALKENES FROM ESTERS 1% Pd2(dba)3-CHCl3 , 2.2 HCOOH 2% chiral phosphine , dioxane -&• l,8-iw-(dimethylamino)naphthalene \yr»nr-n I 20°C , 22h MeO2CU I 96% (85%ee,R) Hayashi. T.: Iwamura, H.; Naito, M.; Matsumoto, Y.; Uozumi, Y.; Miki, M.; Yanagi. K. J. Am. Chem. Soc., 1994, 116, 775

Section 205

Alkenes from Halides

SECTION 204:

221

ALKENES FROM ETHERS, EPOXIDES AND TfflOETHERS

OAc

Te , THF

,OH

LiBHEt3 Ph Ph Dittmer. D.C.: Zhang, Y.; Discordia, R.P. J. Org. Chem., 1994, 59, 1004 Bu3SnH , cat. BEt3

S

QH

toluene, 0°C

Uenishi. J.: Kubo, Y. Tetrahedron Lett., 1994, 35, 6697

i,-78°C -> rt,90min *Bu

Bu

^\s / /

f \ Bu Bii

76%

Doris, E.; Deschoux, L.; Mioskowski, C. Tetrahedron Lett., 1994, 35, 7943 SECTION 205:

ALKENES FROM HALIDES AND SULFONATES

BusSnH , AIBN, Tol, reflux - Pt Ph i U-

j.

x.

I

I

71%

Destabel, C.; Kilbum, J.D.; Knight, J. Tetrahedron Lett., 1993, 34, 3151

I.Li, THF, r t , l h 2.ZnCl 2 ,THF,0 0 C->rt Br

\-j

85%

5% "Pd(PPh3)2", 10h Katz. T.J.: Gilbert, A.M.; Huttenloch, M.E.; Min-Min, G.; Brintzinger, H.H. Tetrahedron Lett. 1993, 34, 3551

222

Compendium of Organic Synthetic Methods, Vol. 9

Br

MeLi , 20°C

Section 206

82%

Bu Br Bu SiMe3 Baird. M.S.: Dale, C.M.; Al Dulayym, J.B. J. Chem. Soc., Perkin Trans. L, 1993, 1373 Ci4H16-

2eq.Me 2 S=CH 2 .THF

-10°C ^ rt Alcaraz, L.; Harnett, J.J.; Mioskowski, C.; Martel, J.P.; Le Gall, T.; Shin, D.-S.; Falck, J.R. Tetrahedron Lett., 1994, 35, 5453 l.CuCN-2LiCl,DMPU -2. E-hexenyl iodide, 60°C , 12h

CgH17ZnI

R

quant. Marquais, S.; Cahiez, G.; Knochel. P. Synlett, 1994, 849 Br ,Ph

SmI2 , THF , 5 min

i

Br Yanada. R.: Bessho, K.; Yanada, K. Chem. Lett., 1994, 1279

Bu3Sn

10% Pd/C, 10% Cul, 20% AsPh3 NMP, 80°C MeO MeO Roth, G.P.; Farina, V.; Liebeskind, L.S.; Pena-Cabrera, E. Tetrahedron Lett., 1995, 36, 2191 EtMgBr, THF, 0°C quant. Ni(dppe)Cl2 Malanga. C.: Aronica, L.A.; Lardicci, L. Tetrahedron Lett., 1995, 36, 9189

SECTION 206: ALKENES FROM HYDRIDES For conversions of methylenes to alkenes (RCH2R1 —> RR'C=CH2), see Section 200 (Alkenes from Alkyls). NO ADDITIONAL EXAMPLES

Section 209

Alkenes from Alkenes

223

SECTION 207: ALKENES FROM KETONES

CC.H; PhMe,50°C e Petasis. N.A.: Bzowej, E.I. Tetrahedron Lett., 1993, 34, 943 (MeO)2POCH2CO2Me

65%

„/ Me

/

\

>CO2Me

85% LiOH , THF, MS , reflux , 4h Bonadies. F.: Cardilli, A.; Lattanzi, A.; Orelli, L.R.; Screttri. A. Tetrahedron Lett., 1994, 35, 3383

Sm,SmI 2 ,CH 3 CHBr 2 cat. CrCl3 , THF, rt

/

*" f'Bu—(\

V

,Me

A=\N 71%

/

H

Matsnhara. S.: Horiuchi, M.; Takai, K.; Utimoto. K. Chem. Lett., 1995, 259 1. EtLi, CeQ3 , THF, -78°C 2. KH , DMF, 50°C Phl

Ph 95% (92:8 E:Z) Bartoli. G.: Marcantoni, E.; Sambri, L.; Tamburini, M. Angew. Chem. Int. Ed. Engl., 1995, 34,2046 Related Methods:

Section 199 (Alkenes from Aldehydes).

SECTION 208: ALKENES FROM NITRILES NO ADDITIONAL EXAMPLES SECTION 209: ALKENES FROM ALKENES I]

O

2% Cl2(PCy3)2Ru=CH-CH=CHPh

PhH, 20°C "~ i Fu, G.C.; Nguyen, ST.; Grubbs. R.H. J. Am. Chem. Soc., 1993, 115, 9856

224

Compendium of Organic Synthetic Methods, Vol. 9

Section 209

, 10%Sc(OTf)3 CH2C12, 0°C , 13h new Diels-Alder catalyst Kobavashi. S.: Hachiya, I.; Araki, M.; Ishitani, H. Tetrahedron Lett., 1993, 34, 3755 x>

>

^^^

\

ArN=Mo(OR)=CHR catalyst l l \ )- OTBS --—----*U> PhH , 20°C , 30 min ^-V

y - OTBS 91%

Fu, G.C.; Grubbs. R.H. J. Am. Chem. Soc., 1993, 115, 3800 ~ +

l%Mo[OC(CF3)2Me]2(NAr)CHCMe2Ph --

Crowe. W.E.: Zhang, ZJ. J. Am. Chem. Soc., 1993, 115, 10998 l.PhBr,THF,Pd(PPh 3 ) 4 NaOH , reflux, 12h 2. NaOH, H2O2 SiMe3 SiMe3 Soderquist J.A.: Colbert, J.C. Tetrahedron Lett., 1994, 35, 27 SmI2 PhH/HMPA, rt, 10 min Ph

Kunishima, M.; Hioki, K.; Tani. S.: Kato, A. Tetrahedron Lett., 1994, 35, 7253 ,O

v

^

.

£>-

8% (PCy3)2Cl2Ru=CHCH=CPh2

O-

*

-**?^.

PhH , 55°C, 3h

75% Miller, S.J.; Kim, S.-H.; Chen, Z.-R.; Ciruhhs. R.H. J. Am. Chem. Soc., 1995, 117, 2108

Section 210

Alkenes from Misc.

1. 5% Pd(PPh3)4 ,4 eq. ZnEt2 ether 2. aq. NH4C1

„-

225

T '

ene reaction

A AcO (96 Oppolzer. W.: Schroder, F. Tetrahedron Lett., 1994, 35, 7935

.

4)

44%

Ni(dppe)Cl2, iPrMgBr, THF Me3SiCl, rt, (seconds)

-O Malanga. C.: Urso, A.; Lardicci, L. Tetrahedron Lett., 1995, 36, 1133 2% (OAr)2Cl2W=O , 90°C , In 1,2,4-trichlorobenzene AT = 2,4-dibromophenyl

68% (97% ee) Nugent. W.A.: Feldman. J.: Calabrese, J.C. J. Am. Chem. Soc., 1995, 117, 8992 REVIEW: "Reagent-Controlled Asymmetric Diels-Alder Reactions," Oh. T.: Reilly, M. Org. Prep. Proceed. Int., 1994, 26, 129

SECTION 210:

ALKENES FROM MISCELLANEOUS COMPOUNDS Q |f

N \

1. BuLi, THF, -78°C 2.C,iH23CQ2Me

v

CnH23

4. Ed

5. CeCl3, NaBH4 6. THF, 105°C , 20h 63x96x93x92% (102:1 E:Z) Denmark. S.E.: Amburgey, J. /. Am. Chem. Soc., 1993, 115, 10386

226

Compendium of Organic Synthetic Methods, Vol. 9

Section 210

70% Gai, Y.; Jin, L.; Julia. M.: Verneaux. J.-N. J. Chem. Soc. Chem. Commun., 1993, 1625 BuLi, 2% Fe(acac)3 0°C -» reflux 79% (76:24 E:Z) Jin, L.; Julia. M.: Verpeaux, J.N. Synlett, 1994, 215 PIT

^S' 02

KOH , A12O3 , CBr2Frr-BuOH

Ph

Chan. T.-L.: Fong, S.F.; Li, Y.; Man, T.-O.; Poon, C.-D. /. Chem. Soc. Chem. Commun., 1994, 1771 O2Ph 8eq. SmI 2 ,THF,DMPU Ph

""

1

35min

Ph

95% Keck. G.E.: Savin, K.A.; Weglarz, M.A. /. Org. Chem., 1995, 60, 3194 ph

(E:Z 9:1)

C9H19 \ X

n ^^P

C9H19

x°Et

Lawesson's reagent, xylene

C9Hi9. *"

OEt

^*^^r

^^ ^^C1 T-T CgHl7

|| reflux, 22h Q quant. Shimagaki. M.: Fujieda, Y.; Kimura, T.; Makata, T. Tetrahedron Lett., 1995, 36, 719 OAc

Mg° , cat. HgCl2, EtOH SO2Ph

T rt,2h

Lee, G.H.; Lee, H.K.; Choi, E.B.; Kim, B.T.; Pak. C.S. Tetrahedron Lett., 1995, 36, 5607 REVIEW: "Rare Earth Metal Trifluoromethanesulfonates as Water-Tolerated Lewis Acid Catlaysts in Organic Synthesis," Kobavashi. S. Synlett, 1994, 679

Section 213

Oxides from Alcohols

227

CHAPTER 15 PREPARATION OF OXIDES This chapter contains reactions which prepare the oxides of nitrogen, sulfur and selenium. Included are W-oxides, nitroso and nitro compounds, nitrile oxides, sulfoxides, selenoxides and sulfones. Oximes are considered to be amines and appear in those sections. Preparation of sulfonic acid derivatives are found in Chapter Two and the preparation of sulfonates in Chapter Ten.

SECTION 211: OXIDES FROM ALKYNES .OTBS

1. ClPPhz , NEt3 , THF , -78°C

99x?%

'CO2Me

Grissom. J.W.: Slattery, B.J. Tetrahedron Lett., 1994,35, 5137 SECTION 212: OXIDES FROM ACID DERIVATIVES

2(1

95%

Neumann. W.P.: Wicemec, C. Chem. Ber., 1993, 126, 763 SECTION 213: OXIDES FROM ALCOHOLS AND TfflOLS

O CH2C12 2. air Gu, D.; Harpp. D.N. Tetrahedron Lett., 1993, 34, 67

SO2H

74%

228

Compendium of Organic Synthetic Methods, Vol 9

Section 219

SECTION 214: OXIDES FROM ALDEHYDES NO ADDITIONAL EXAMPLES SECTION 215:

OXIDES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES

SECTION 216: OXIDES FROM AMIDES NO ADDITIONAL EXAMPLES SECTION 217: OXIDES FROM AMINES PIT

N

Ph

0,05Pr4NRuO 4) 1.5NMO

OH

MeCN , rt , 2d

75% (>50:1 Z:E) Goti. A.: De Sarlo, F.; Romani, M. Tetrahedron Lett., 1994, 35, 6571 Oxone®

CO2H

aq. acetone Webb. K.S.: Seneviratne, V. Tetrahedron Lett., 1995, 36, 2377 SECTION 218: OXIDES FROM ESTERS Na$O2Tol , THF 0.01Pd(PPh3)4,rt OAc chiral phosphine , 72h

SO2Tol

OS(=O)Tol :

1) 83%

Eichelmann, H.; Gais. H.-J. Tetrahedron Asymmetry, 1995, 6, 643 SECTION 219:

o

OXIDES FROM ETHERS, EPOXIDES AND THIOETHERS 5% TPAP, 3 eq. NMO MeCN,30°C,4AMS,2h *"

= (n-Pr>4NRuO4 Guertin, K.R.; Kende. A.S. Tetrahedron Lett., 1993, 34, 5369

\c'/X

cAo

92%

Section 219

Oxides from Ethers

229

?

C(NO2)4,hv(Pyrex)

CH2Ch 92% Ramkumar, P.; Sankararaman. S. Synthesis. 1993, 1057 O

o Ph^ °"^ Me

H2O2, MeCN, K2CQ3

•-

o Ph-" ^ Me

MeOH , 0°C, 2h Page. P.C.B.: Graham, A.E.; Bethell, D.; Park, B.K. Synth. Commun., 1993, 23, 1507 „ Ph—^\

MnO 2 , Me3SiCl, MeOH

^

Me

P II Ph^S\

99%

Bellesia, F.; Ghelfi. F.: Pagnoni, U.M.; Pinetti, A. Synth. Commun., 1993, 23, 1759 r-BuOOH , H2O , 70°C , 30 min

Q S Bu ^Bu Frinenelli. F.: Pellegrino, R.; Pizzo, F. Synth. Commun., 1993, 23, 3157 B

U ^ B u

*"

quant.

O cyclohexanone monooxygenase

73% (99% ee, R) Secundo, F.; Carrea. G.: Pallavalle, S.; Franzosi, G. Tetrahedron Asymmetry, 1993, 4, 1981 Me

.
1.35 eq. oxone rt,1.2h

»

with 0.65 eq. Oxone - obtain 47% sulfoxide Webb. K.S. Tetrahedron Lett., 1994, 35, 3457

Ph^

^S^

1.1

33%

- X '%C3F3 t >F C p 49

CHC13 , CFC13 , -40°C

O II rn

VSXXa\

with 2.7 eq., obtain the sulfone (91%) PesMarteau. P.P.: Petrov, V.A.; Montanaari, V.; Pregnolato, M.; Resnati. G. J. Org. Chem., 1994, 59, 2762

230

Compendium of Organic Synthetic Methods, Vol 9

Section 219

NaIO4, cat. RuCl3«H2O Ph-~";>""-Ph

Ih Su. W. Tetrahedron Lett., 1994, 35, 4955

quant.

NHAc

NHAc

NHAc

mcpba

(8 : Glass. R.S.: Singh, W.P.; Hay, B.A. Tetrahedron Lett., 1994, 35, 5809

1. ^^

H2O2 , ether, DBU, -28°C (-)-camphorsulfonylimine

f

Me

Ph. .S, 2. aq. Na sulfite ^-^ Me quant (35% ee, R) Page. P.C.B.: Heer, J.P.; Bethell, D.; Collington, E.W.; Andrews, D.M. Tetrahedron Lett., 1994, 35, 9629

NaOCl, TEMPO, KBr

°

Bu^NCl, CH£\2, satd. NaHCO3 Siedlecka, R.; Skarzewski. J. Synthesis. 1994, 401

PIT

.x^>\

PhIO, cat. TsOH, MeCN , 25°C Me

° II ^S^

^

Ph

82%

Me

Cavicchioni. G. Synth. Commun., 1994, 24, 2223 1. MnO2-35% aq. HC1, MeOH 0°C -> 10°C,0.75h

99% 2.NaOH Ph^ Me Fabretti, A.; Ghelfi, F.; Grandi. R.: Pagnoni, U.M. Synth. Commun., 1994, 24, 2393 i U

AVJAS

^^ fcJ^^

NaBrO2, rt, wet zeolite F-9

9

CH 2 Cl 2 ,lh Ph— S ^Me Hirano, M.; Kudo, H.; Morimoto. T. Bull. Chem. Soc. Jpn., 1994, 67, 1492

82%

Section 219

Oxides from Ethers

231

PhIO, MeCN, Ih 10% Mn salen catalyst

^-S.w

o

||

Me

Ph-~

57% (62% ee, R) Noda, K.; Hosoya, N.; Irie, R.; Yamashita, Y.; Katsuki. T. Tetrahedron, 1994, 50, 9609

p-Tol^"*"S""^Me

chiral oxaziridine, CH2jCl2 *0°C

I? 'I p-Tol-*"'Me

70% ee Jennings. W.B.: Kochanewyczm, M.J.; Lovely, C.J.; Boyd, D.R. J. Chem. Soc. Chem. Commun., 1994, 2569

o

PhMe2COOH, Ti(OiPr)4, H2O

II

77%

Me

(RR)-DET, CH2C12,-20°C Ph^ Me (99%ee'R) Brunei, J.-M.; Diter, P.; Duetsch, M.: Kagan. H.B. J. Org. Chem., 1995, 60, 8086 O II 84% /S\ Bu Bu Suarez, A.R.; Rossi, L.I.; Martin, S.E. Tetrahedron Lett., 1995, 36, 1201 ^S^ Bu^ Bu

1.5 M HNO 3 ,1 % FeBr3 , 30 min

SiO2, CH2C12, f-BuOOH

s Bu/

^

Bu

30^i

"

j? S

_ / \R Bu Bu

86%

with 2 eq. f-BuOOH, obtain 83% of sulfone Breton, G.W.; Fields, J.D.; Kropp. P.J. Tetrahedron Lett., 1995, 36, 3825 cyclohexanone monooxygenase

^^^\ ,—

O 97% (54% ee, R) Pasta. P.: Carrea, G.; Holland, H.L.; Dallavalle, S. Tetrahedron Asymmetry, 1995, 6, 933

s Pn-- \

O2, m-xylene, Mn (III) salen complex ^

Jl Ph

66%(51%ee)

r-BuCHO,rt ^Me Nagata, T.; Imagawa. K.: Yamada, T.; Mukaiyama, T. Bull. Chem. Soc. Jpn., 1995, 68, 3241

232

Compendium of Organic Synthetic Methods, Vol 9

Section 222

SECTION 220: OXIDES FROM HALIDES AND SULFONATES Phi, Cul, DMF, heat PhSC^Na Suzuki. H.: Abe, H. Tetrahedron Lett., 1995, 36, 6239

*-

PhSO2Ph

SECTION 221: OXIDES FROM HYDRIDES NO2-O3, CH2C12

\ /

-10°C, 3h

51% (57:2:41 o:m:p) Suzuki. H.: Murashima, T.; Kozai, I.; Mori, T. J. Chem. Soc., Perkin Trans. 1., 1993, 1591 Suzuki. H.: Mori, T. J. Chem. Soc., Perkin Trans. 1., 1995, 291 From aryl esters: meta-nitro is the major product Suzuki. H.: Tomaru, J.-i.; Murashima, T. / Chem. Soc., Perkin Trans. L, 1994, 2413 From aryl acetates: orthorpara predominates (60:40) Suzuki. H.: Tatsumi, A.; Ishibashi, T.; Mori, T. J. Chem. Soc., Perkin Trans. 1., 1995, 339 NO2-O3, MeCN, MgO, 0°C

R

R = Et 95% (14:31:55 o:m:p) R = H 0% Suzuki. H.: Yonezawa, S.; Mori, T. Bull. Chem. Soc. Jpn., 1995, 68, 1535 REVIEW: "Ozone-Mediated Nitration of Aromatic Compounds with Lower Oxides of Nitrogen," Mori, T.: Suzuki. H. Svnlett. 1995, 383

SECTION 222: OXIDES FROM KETONES

O

l.NH 2 OH,PtCl,KOH 2. CF3CO3H

(1:13 exo:endo) Olah, G.A.; Ramaiah, P.; Prakash. C.K.S.7. Org. Chem., 1993, 58, 763

Section 225

Oxides from Misc.

233

SECTION 223: OXIDES FROM NITRILES

hv (254 nm) 55%

MeCN, 25,C , 2h Li, C.; Fuchs. P.L. Tetrahedron Lett., 1993, 34, 1855 SECTION 224: OXIDES FROM ALKENES

toluene, AIBN (syringe pump) Balczewski, P.; Mikotajczyk, M. Synthesis, 1995, 392 SECTION 225:

[f

Q

„«„

OXIDES FROM MISCELLANEOUS COMPOUNDS P

PhMgBr, THF, 25°C

|f Ph

71%

Ph Ph Cardellicchio, C.; Fiandanese, V.; Naso. F.: Pietrusiewicz, K.M.; Wi£iewski, W. Tetrahedron Leu., 1993, 34, 3135

PhCHO °'5M

Me2N

(9 : 91) 84% Denmark. S.E.: Griedel, B.D.; Coe, D.M. J. Org. Chem., 1993, 58, 988

234

Compendium of Organic Synthetic Methods, Vol 9

l.LiNAPH 2.

Section 225

PhO

Br,.

PhYu, J.; Cho, H.-S.; Chandrasekhar, S.; Falck. J.R.: Mioskowski. C. Tetrahedron Lett., 1994, 35, 5437

1? THF.rt Ph

Yl 61%

(>98% ee, S) Cardellicchio, C.; Fiandanese, V.; Naso. F.: Pacifico, S.; Koprowski, M.; Pietrusiewicz. K.M. Tetrahedron Lett., 1994, 35, 6343

Section 302

Alkyne - Alcohol

235

CHAPTER 16 PREPARATION OF COMPOUNDS

DIFUNCTIONAL

SECTION 300: ALKYNE - ALKYNE 1. NaNTMS2; NBS 2. f-BuOC^CH, CuCl EtNH2, NHP DMF, 23°C
SiMe^-Bu

Y

>

^=

N

^s

Of-Bu

SiMe^-Bu

•OMe '—OMe 35% Magriotis. P.A.: Vourloumis, D.; Scott, M.E.; Tarli, A. Tetrahedron Lett., 1993, 34, 2071 SECTION 301: ALKYNE - ACID DERIVATIVES NO ADDITIONAL EXAMPLES SECTION 302: ALKYNE - ALCOHOL, THIOL

)H

,CHO

^^

ether, 25°C, 15 min

*^^^

82%

2. H2O2 , NaOH Brown. H.C.: Khire, U.R.; Racherla, U.S. Tetrahedron Lett., 1993, 34, 15 \ \ == Bu ^\ / 3.iPrCHO / \ ' OH (98:2 anti:syn) Katsuhira, T.; Harada. T.: Maejima, K.; Osada, A.: Oku. A. / Org. Chem., 1993, 58, 6166

\ /

1. Bu^Znl,-85°C -» 0°C 2.3eq.ZnCl 2

236

Compendium of Organic Synthetic Methods, Vol 9

Section 302

Ph

SbBu4

PhCHO, -78°C BuLi/THF/hexane

SiMe3

'SiMe3 (94 : 6) 80% Zhang, L-T.; Mo, X-S.; Huang, J-L.; Huang. Y.-Z. Tetrahedron Lett., 1993, 34, 1621 1.2eq.LDA,THF,-100°C 2.2eq.PhCHO,THF

OH

3. NaH ,THF , 0°C

~"^

\

Ph

83% (>99%ee, S) Kusuda, S.; Kawamura, K.; Ueno, Y.; Toru. T. Tetrahedron Lett., 1993, 34, 6587 I? c

1.3exj.f-BuLi 2. EtCHO , -78°C ->• -30°C

^V

Cl' " Ph 67% Satoh, T.; Hayashi, Y.; Yamakawa. K. Bull. Chem. Soc. Jpn., 1993, 66, 1866 CHO

^»««SiMe2Ph 1. 0-DCB , reflux 2.TBAF

^ ^xVOH 49%

Jin, J.; Smith, D.T.; Weinreb. S.M. 7. Org. Chem., 1995, 60, 5366 (PhCsQ2AlEt2' Na+

^v^ ( Tol '°° C ' lh OH Ahn, J.H.; Joung, M.J.; Yoon. N.M. J. Org. Chem., 1995, 60, 6173 PhCHO

^

===

Pb

95%

OH BiT^Bu C8H17

==

1

^

SmI2,HMPA/PhH

CgH17

^

/ D (— Bu

\

Bu 78% Kunishima, M.; Tanaka, S.; Kono, K.; Hioki, K.; Tani. S. Tetrahedron Lett., 1995, 36, 3707

Section 305

Alkyne - Amine

237

/un

r-BuCHO, GaI3 , NEt3 Ph

3=

H

-

Ph

==

/

THF.rt

r-Bu

80%

Han, Y.; Huanap. Y.-Z. Tetrahedron Lett., 1995, 36, 7277 PhCHO

Ph

SnBu3

Ph

\ ) H(f

*•

InCl 3 , MeCN, 25°C , 30 min

= Ph

92% Yasuda, M.; Miyai, T.; Shibata, I.; Baba. A.: Nomura, R.; Matsuda, H. Tetrahedron Lett., 1995, 36, 9497

PhCHO , Zn , THF

+ Ph

satd. NH^Cl, rt

*"^ ^=

Ph

(89 : Yavari. I.: Riazi-Kermani, F. Synth. Commun., 1995, 25, 2923

11) 68%

SECTION 303: ALKYNE - ALDEHYDE SPh 1.SO2C12,CC14,00C _ _ / -—-—-- Ph-==- CHO Ph 2. CuCl2 , Fortes. C.C.: Garrote, C.F.D. Synth. Commun., 1993, 23, 2869 _

SECTION 304: ALKYNE - AMIDE NO ADDITIONAL EXAMPLES SECTION 305: ALKYNE - AMINE xxCsHij y ii

2Et 2 NH 2 ,l%CuCl

<

X THF, 50°C, 2h O Imada, Y.; Yuasa, M.; Nakamura, I.; Murahashi. S.-I. J. Org. Chem., 1994, 59, 2282

Ph

/^

Fff

=

SiMe3 Ph,

Wu. M.-J.: Yan, D.-S.; Tsai, H.-W.; Chen, S.-H. Tetrahedron Lett., 1994, 35, 5003

47%

238

Compendium of Organic Synthetic Methods, Vol 9

Br '

Section 307

BuNH 2 , 3% CuBr, MeCN x

'

90%

NHBu Geri, R.; Polizzi, C.; Lardicci, L.: Canorusso. A.M. Gait. Chim. Ital, 1994, 224, 241

-TMS ,DMF Pd2(dba)3-CHCl3, P(0-Tol)3 iPr2NEt Okita, T.; Isobe. M. Tetrahedron, 1995, 51, 3737 SECTION 306: ALKYNE - ESTER NO ADDITIONAL EXAMPLES SECTION 307: ALKYNE - ETHER, EPOXIDE, THIOETHER

i

— PhSeSePh Ph C=C—Br — »Ph C=C—SePh 75% Cul, HMPA Braga. A.L.: Reckziegel, A.; Menezes, P.H.; Stefani, H.A. Tetrahedron Lett., 1993, 34, 393 PhSeBr, Cul, DMF C55Hif == H ^ C55 H,f = SPh U " 82% Braga. A.L.: Silveira, C.C.; Reckziegel, A.; Menezes, P.H. Tetrahedron Lett., 1993, 34, 8041 PhI(OAc)2, PhSeSePh, CH2C12 -

Ph

=

SePh

40°C 81%

Tingoli. M.: Tiecco, M.; Testaferri, L.; Balducci, R. Synlett, 1993, 211 HO

DBU, CuCl2-2 H2O , 0°C

\\

' 83% Godfrey Jr.. J.D.: Mueller, R.H.; Sedergran, T.C.; Soundararajan, N.; Colandrea, V.J. Tetrahedron Lett., 1994, 35, 6405

Section 311

Alkyne - Alkene

239

SECTION 308: ALKYNE - HALIDE Br

DMSO, 15°C DBU

ii

,

go%

Ratovelomanana. V.: Rollin, Y.; G6b6henne, C.; Gosmini, C.; Penchon, J. Tetrahedron Lett., 1994, 35, 4777 © © (collidine)2I PF6

Ph—=—H

ph

=

l

75%

CH2Cl2 Brunei, Y.; Rousseau. G. Tetrahedron Lett., 1995, 36, 2619

SECTION 309: ALKYNE - KETONE

l

' Ph'

i

2.FVP(500*C)

72% x 82% Aitken. R.A.: H6rion, H.; Janosi, A.; Raut, S.V.; Seth, S.; Shannon, I.J.; Smith, F.C. Tetrahedron Lett., 1993, 34, 5621

SECTION 310: ALKYNE - NITRILE 1. CuCN, TMSC1, H2O DMSO , MeCN, 72h Ph

H

2. cat. Nal, 50°C Luo. F.-T.: Wang, R.-T. Tetrahedron Lett., 1993, 34, 5911

Ph

CN

SECTION 311: ALKYNE - ALKENE ,C02Me

IQ

™^>™%^

96%

Mandai. T.: Tsujiguchi, Y.; Matsuoka, S. Tetrahedron Lett., 1993, 34, 7615

/2/0

240

Compendium of Organic Synthetic Methods, Vol 9

Section 311

Bu3S • SiMe3

<^\ \ ff~~~-

COzEt

*-<

Pd(dba)2, Ph3As NMepyrrolidone, 40°C

OTf

2. aq. HC1 Lipshutz. B.H.: Alami, M. Tetrahedron Lett., 1993, 34, 1433

C5Hn

==

H

/

Bir

0.05 Pd(PPh)4,0.1 Cul 2eq.NEt 3 ,PhH,lh _ „ /

91%

Gueugnot, S.; Linstrumelle, G. Tetrahedron Lett., 1993, 34, 3853 °H

C5HU

QsHn , Pd(PPh3)4,15 min H 93% Alami. M.: Ferri, F.; Linstrumelle. G. Tetrahedron Lett., 1993, 34, 6403 Ph 1. norbornadiene, B"3Sn 1% PdCl2(PPh3)2, 80-100°C, 20h

Phi

^

2. heat

54%

Kosuei. M.: Kimura, T.; Oda, H.; Migita, T. Bull. Chem. Soc. Jpn., 1993, 66, 3522 l.C^n,Pd(PPh 3 ) 4 ,CuI BuNH 2 ,rt Cl

Cl

/

\

72%

2. PdCl^PhCNk, piperidine rt

Alami. M.: Crousse, B.; LinstrumeUe, G. Tetrahedron Lett., 1994, 35, 3543 FVP(500°C)

*

Ph

Ph 59% Aitken. R.A.: Boeters, C.; Morrison, J.J. J. Chem. Soc., Perkin Trans. 1., 1994, 2473

Section 314

Acid - Aldehyde

241

l.sec-BuLi,THF,-45°C 2.ZnBr2 -45°C -* 20°C 3. H3O+ •SiMe3 Meyer, C.; Marek. I.: Normant. J.-F.: Platzer, N. Tetrahedron Lett., 1994, 35, 5645 Ph

5% HRh(CO)(PPh3)3 35% PEt3 Bu

H +

THF, reflux , 9h 68% (>20:1 endo:exo) (>20:1E:Z) Ph' Yamaguchi. M.: Omata, K.; Hirama, M. Tetrahedron Lett., 1994, 35, 5689 \ Ph

=

ci .Dibal.THF

SnBu33 Ni(acac)2, P(OEt)3 , reflux

Ph

^

'

77%

Cui, D.-M.; Hashimoto, N.; Ikeda. S.: Sato, Y. J. Org. Chem., 1995, 60, 5752

SECTION 312: CARBOXYLIC ACID - CARBOXYLIC ACID NO ADDITIONAL EXAMPLES SECTION 313: CARBOXYLIC ACID - ALCOHOL, THIOL

Me2HG

^

/)

<(

CFC13, THF, -5°C »_ 2.aq.HCl Me2H

62% Garcia, M.; del Campo, C.; Sinisterra, J.V.; Llama. E.F. Tetrahedron Lett., 1993, 34, 7973

SECTION 314: CARBOXYLIC ACID - ALDEHYDE NO ADDITIONAL EXAMPLES

242

Compendium of Organic Synthetic Methods, Vol 9

Section 316

SECTION 315: CARBOXYLIC ACID - AMIDE Me

-^ FaC

n

o

Kazmaier. IT.: Maier, S. /. Chem. Soc. Chem. Commun., 1995, 1991 5 eq. LDA, 2.5 eq. quinone Al(OiPr)3 WAHN

••

TPAHN

" 70% (98% ds/86% ee) Kazmaier. U.: Krebs, A. Angew. Chem. Int. Ed. Engl., 1995, 34, 2012 SECTION 316: CARBOXYLIC ACID - AMINE l.PhMgBr,THF,-40°C 2. TFA, CH2C12

f, Jl

ft \

CO2Et 3. DDQ, CH2C12 4.10% NaOH , reflux

H

83x72x93% Ezquerra. J.: Pedregal, C.; Rubio, A.; Valenciano, J.; Navio, J.L.G.; Alvarez-Builla, J.; Vaquero, LL Tetrahedron Lett., 1993, 34, 6317

2.: „ 84% (35:65 syn:anti) Mladenova. M.: Bellassoued, M. Synth. Commun., 1993, 23, 725

Section 318

Acid - Ether

243

1. PHCHO P 0.1 [Au(c-hexNC)2]BF4 \ ^

bisphosphinoferrocene derivative, 25°C, 40h 2.6NHC1

Hr/ HU (94

Soloshonok, V.A.; Havashi. T. Tetrahedron Lett., 1994, 35, 2713 1. oxalyl chloride, ether 2. satd. NaHCO3 , reflux 3. TsNHNH2, reflux 4.NaBH 4 ,THF

^ ^^w

98x39%

Guan, X.; Borchardt. R.T. Tetrahedron Lett., 1994, 35, 3013 REVIEWS: "Recent Developments in the Stereoselective Synthesis of a-Amino Acids," Duthaler. R.O. Tetrahedron, 1994, 50, 1539 "Recent Stereoselective Synthetic Approaches to p-Amino Acids," Cole. D.C. Tetrahedron, 1994, 50, 9517 Related Methods:

Section 315 (Carboxylic Acid - Amide). Section 344 (Amide - Ester). Section 351 (Amine - Ester).

SECTION 317: CARBOXYLIC ACID - ESTER NO ADDITIONAL EXAMPLES SECTION 318:

CARBOXYLIC ACID - ETHER, EPOXIDE, TfflOETHER

CO2H (85

Mead. K.T.: Pillai, S.K. Tetrahedron Lett., 1993, 34, 6997

:

CO2H 15) 82%

244

Compendium of Organic Synthetic Methods, Vol 9

Section 322

SECTION 319: CARBOXYLIC ACID - HALIDE, SULFONATE I/~V TT

'-'2"

f^f\

1.2.2 eq. .yec-BuLi/TMEDA THF,-90°C 2.4 eq. C13CC13 , THF, -78°C 3.4NHC1

T_I

y^'2"

II

I

71%

F

Moyroud, J.; Guesnet, J.-L.; Bennetau, B.; Mortier. J. Tetrahedron Lett., 1995, 36, 881 SECTION 320: CARBOXYLIC ACID - KETONE

Na , n-C3H7OH , reflux

\

98%

(>98%ee)

H211/ \ Moody, H.M.; Kaptein. B.: Broxterman, Q.B.; Boesten, W.H.J.; Kamphuis, J. Tetrahedron Lett., 1994, 35, 1777

0.5 Cu(ClO4)2-6 H2O O2 , MeCN , rt , 10-15 h OH O 96% Cossv. J.: Belotti, D.; Bellosta, V.; Brocca, D. Tetrahedron Lett., 1994, 35, 6089

Also via: Section 360 (Ketone - Ester). SECTION 321: CARBOXYLIC ACID - NITRILE NO ADDITIONAL EXAMPLES Also via:

Section 361 (Nitrile - Ester).

SECTION 322: CARBOXYLIC ACID - ALKENE 1. CF2=CHLi 2. H3O+ 3.H30+ Tellier. F.: Sauvetre, R. Tetrahedron Lett., 1993, 34, 5433

60% (E)

Section 323

Alcohol - Alcohol

245

0.1 PCy3 , 3 TESC1

*" 2.5DBU,MeCN

C3H

Hanamoto, T.; Baba, Y.; Inanaga. J. J. Org. Chem., 1993, 58, 299 MnZnBr, ether 0

"~

-"

C02H

80%

Duchene. A.: Abarbi, M.; Parrain, J.-L.; Kitamura, M.; Noyori, R. Synlett, 1994, 524 Also via:

Section Section Section Section

313 (Alcohol - Carboxylic Acids). 349 (Amide - Alkene). 362 (Ester - Alkene). 376 (Nitrile - Alkene).

SECTION 323: ALCOHOL, THIOL - ALCOHOL, THIOL ^

OH

.CHO

SmI 2 ,THF PhCHO

OH 97% in THF + 2.8 eq. HMPA 10% Shiue, J-S.; Lin, C-C.; Fane. J-M. Tetrahedron Lett., 1993, 34, 335

60%

K3Fe(CN)6,K2C03 f-BuOH , H 2 0,12h

Bu

SiMe3

ODHQ ^ J^

_

HO'

> (89% ee)

DHO = dihydroquinidine ODHQ Soderquist. J.A.: Rane, A.M.; L6pez, C.J. Tetrahedron Lett., 1993, 34, 1893

Ph

°\xx

AD-mix-B

—^

r-BuOH, H 2 0,0°C

OH

1

PnOv^^xX^x011

Wang, Z-M.; Zhang, X-L.; Sharpless. K.B. Tetrahedron Lett., 1993, 34, 2267

SiMe3

246

Compendium of Organic Synthetic Methods, Vol 9

Section 323

Me

Rh+2 cat., Cs2CO3 , PhBr ^, 25°C -» 90°C OH Me Barrett A.G.M.: Itoh, T.; Wallace, E.M. Tetrahedron Lett., 1993, 34, 2233 Ph

-

J

1.2eq.SmBr2 2 H

' '°

A

OH Lebrun, A.; Namy. J-L.: Kagan. H.B. Tetrahedron Lett., 1993, 34, 2311

°H »»

DHQ-CLB Me3Sis^

.x^ ^CsHn

^ Me3Si

93%(71%ee,R) OH Okamoto, S.; Tani, K.; Sato. F.: Sharpless. KB.: Zargarian, D. Tetrahedron Lett., 1993, 34, 2509 iSH , NEt3 , MeOH 1. TB AF, AcOH

SH

ptfx^

H

^^X'°H

(7 Britain, J.; Gareau. Y. Tetrahedron Lett., 1993, 34, 3363

pj

:

1)

87%

H 2 O,10KBar,60°C,ld

93% (49% ee) Kotsuki. H.: Kataoka, M.; Nishizawa, H. Tetrahedron Lett., 1993, 34, 4037 !%OsO 4 ,l% catalyst catalyst = bis-dihydroquinolyl derivative

98% ee, R OH

Crispino, G.A.; Jeong, K.-S."; Kolb, H.C.; Wang, Z.-M.; Xu, D.; Sharpless. K.B. J. Org. Chem., 1993, 58, 3785

Section 323

Alcohol - Alcohol

247

OH

«

OH

1.10% Cp£rCl2 , ether 2. 5 eq. EtMgCl, 25°C, 12h 3. O 2 ,08C

^.XX^

Et

70% (98:2 syn:anti) Hovevda. A.H.: Morken, J.P. J. Org. Chem., 1993, 58, 4237 Oallyl

'V 5% >L ^^"

, 1% Os04, rt, 3 K2C03

(Jn

Oallyl

3K3Fe(CN)6,3MeS02NH2,f-BuOH-H20 82% (39% ee, R) Morikawa, K.; Park, J.; Andersson, P.O.; Hashiyama, T.; Sharpless. K.B. J. Am. Chem. Soc., 1993, 115, 8463

1 . Li powder , CH2C12 5% 4,4'-di-r-Bubiphenyl CHO

2.H2O 52%

Guijarro, A.; Yus. M. Tetrahedron Lett., 1994, 35, 253 'H

l.O 2 ,PPh 33,hv,-15°C , 2. PPh3,0°C

Me

(95 : Adam. W.: Gevert, O.; Klug, P. Tetrahedron Lett., 1994, 35, 1681

OH ,Ph

AD-mix B , aq. J-BuOH, 0°C

^-^

-v"

ee,2S,3R) OH Walsh, PJ.; Ho, P.T.; King, S.B.; Sharpless. K.B. Tetrahedron Lett., 1994, 35, 5129

75%

248

Compendium of Organic Synthetic Methods, Vol 9

OH

OH

Section 323

OH

JPrCHO,-78°C

iPr

y/>

[

\

Bx

O

f-ncy 95:5syn:anti *> (94%ee,syn)

_ 1t7 Zl/0

w

50% ee, S

H

Kaneko, Y.; Matsuo, T.; Kivooka. S. Tetrahedron Lett., 1994, 35, 4107 OTMS Yb-TMS-Br THF-HMPA TMSO Taniguchi. Y.: Nakahashi, M.; Kuno, T.; Tsuno, M.; Makioka, Y.; Takaki. K.: Fujiwara. Y. Tetrahedron Lett., 1994, 35, 4111

Me

57% (4:1 syn:anti) Newcomb. M.: Dhanabalasingam, B. Tetrahedron Lett., 1994, 35, 5193 0.1 K20s04,3 K3Fe(CN)6,3 K2CO3 0°C, 12h

OH ^ Ph

Ph

R = cinchonidine derivative ("% ee) Corev. E J.: Noe, M.C.; Grogan, MJ. Tetrahedron Lett., 1994, 35, 6405

2 f-BuCHO

NbCl 3 ,THF,rt -HO

r-Bu

71% (>95:5 d,l:meso) Szvmoniak. J.: Besanfon, J.; Moi'se, C. Tetrahedron, 1994, 50, 2841

Section 323

Alcohol - Alcohol

249

Al, KOH , MeOH , it, 5 min PhCHO

OH Khurana. J.M.: Sehgal, A. J. Chem. Soc. Chem. Commun., 1994, 571 l.d!pc2BH, ether, -78°C 2. PbCHO, -78°C 3. NaOH, H2O2

Ph

•O

| OH

76% (>95%ee) Brown. H.C.: Narla, G. / Org. Chem., 1995, 60, 4686

Ph

Ph

M

H-V°

°

BH3 , THF

(16:84 meso:RR+SS (99% ee SS) Ouallich. G.J.: Keavey, K.N.; Woodall, T.M. Tetrahedron Lett., 1995, 36, 4729 BusSnH , PhH , 20°C

CHO

hV

46% (98:1 cis:trans) Hays, D.S.; Fu. G.C. J. Am. Chem. Soc., 1995, 117, 7283 Ph

*

e' , f-BuOH, H 2 O, K3Fe(CN)6

^ K2CO3 , (DHQD^PHAL , K2OsO2)OH)4

PH Pn.

95% (97% ee, R) Torii, S.; Liu, P.; Tanaka, H. Chem. Lett., 1995, 319 REVIEWS: "Synthesis of a,
250

Compendium of Organic Synthetic Methods, Vol 9

Section 325

"The Oxygenation of Vinyl Cyclopropanes as an Entry Into Stereoselective 1,3-Diol Synthesis," Feldman. K.S. Synlett. 1995, 217 "Catalytic Asymmetric Dihydroxylation," Kolb, H.C.; Van Nieuwenhze, M.S.; Sharpless. Rev., 1994, 94,, 2483 Also via:

Section 327 (Alcohol - Ester).

Section 357 (Ester - Ester).

SECTION 324: ALCOHOL, THIOL - ALDEHYDE H

1. PhCHO, NEt3

Q V \ CHO + / C02H 2.H30+ p/ / 51% Barco, A.; Benetti, S.; De Risi, C.; Pollini, G.P.; Spalluto, G.; Zanirato, V. Tetrahedron Lett., 1993, 34, 3907 *~

[RhCl(CO)2l2,1-methylpyrazole O

HSiMe2Ph, CO (50 atm) Fukumoto, Y.; Chatani, N.; Murai. S. J. Org. Chem., 1993, 58, 4187 Ph3P=CHOMe, CHC13 ,25»C CHO C6H13 Yu, L.; Wang. Z. J. Chem. Soc. Chem. Commun., 1993, 232 Related Melhods:

Section 330 (Alcohol - Ketone).

SECTION 325: ALCOHOL, THIOL - AMIDE l.EtCHO,Li(powder) 3% C10H8, THF 2.H20

/

\

71%

(1 Ram6n, D.J.; Yus. M. Tetrahedron Lett., 1993, 34, 7115

£JHTs 1

- aq. NaOH, 100°C

T' ' 95% 'OH

Moulines. J.: Bats, J-P.; Hautefaye, P.; Nuhrich, A.; Lamidey, A-M. Tetrahedron Lett., 1993, 34, 2315

Section 325

Alcohol - Amide

251

OH

MeSO2NH2, r-BuOH , H2O rt, AD-mix-p™

NEt2 <96%ee)

OH AD-mix-p™= 5% DHQD2-PHAL (chichona alkaloid-phthalzine reagent), 2% K2OsO2(OH)4 Bennani, Y.L.; Sharpless. K.B. Tetrahedron Lett., 1993, 34, 2079 1. Dibal,-78°C NHCbz

'

\ '

OH V "" ^H ^\ . . ^C02Me + \ ^ ^ x

/°™s

IT 1

/C /\

II 1

OMe

/\ /\

NHCbz 7

NHCbz '

3.TiCl2(OiPr)2 Kivooka. S.: Suzuki, K.; Shirouchi, M.; Kaneko, Y.; Tanimori, S. Tetrahedron Lett., 1993, 34, 5729 £HO Me2CuLi,-55°C

BccmrA

--

Me

PH

BocHN

PH

V-<

+

V- (

BocHN Me

Me

Me

(96 : Reetz. M.T.: Rolfmg, K.; Griebenow, N. Tetrahedron Lett., 1994, 35, 1969

Me 4) 84%

1. BuLi , -78°C 2. LiNaphth , -78°C

NHBz •a

3. PhCHO

(1 Foubelo, F.; Yus. M. Tetrahedron Lett., 1994, 35, 4831 l.LDA,THF,-78°C 2.CeCl3,THF,rt O 3. PhCHO , THF , -78°C Shang, X.; Liu. H.-J. Svnth. Commun., 1994, 24, 2485

Me,

1) 72%

:

Ph

OH

O

AOH

MeAlQ2

Me

Me H (97 : 3) 66% Taniguchi, M.; Fujii, H.; Qshima. K.: Utimoto. K. Bull. Chem. Soc. Jpn., 1994, 67, 2514

252

Compendium of Organic Synthetic Methods, Vol 9

Section 326

H ° 86% O Dittami. J.P.: Xu, F.; Qi, H.; Martin, M.W.; Bordner, J.; Decosta, D.L.; Kiplinger, J.; Reiche, P.; Ware, R. Tetrahedron Lett., 1995, 36, 4197

(CH2O)n, acetone, K2CO3 I

H2O, ultrasound

H

^O Jouglet, B.; Oumoch, S.; Rosseau. G. Svnth. Comtnun., 1995, 25, 3869

SECTION 326: ALCOHOL, TfflOL - AMINE . LDA, TiCl2
.

Et02(T

Ptr

ft

"V" _ OH

^ EtO

(>99

Kanemasa . S.: Mori, T.; Wada, E.; Tatsukawa, A. Tetrahedron Lett., 1993, 34, 677 OH

2 TsNCO, THF, Id .Ph

reflux °!5^~X--6

OH Xu, D.; Sharpless. K.B. Tetrahedron Lett., 1993, 34, 951

, SnCl4 CH 2 Cl 2 ,0°C,30min ~^ 2. TBAF.THF

81%

H(

EtOzCBnN

"OMe

(1 : Hioki. H.: Okauda, M.; Miyagi, W.; Ito, S. Tetrahedron Lett., 1993, 34, 6131

»<

Section 326

Alcohol - Amine

Bn

*• |

253

, BF3OEt2 CH2C12 -78°C -

|

Sn6u3 SnBu3

2. iPrCHO, BF3»OEt2 -78°C, 6h

74%

Keck. G.E.: Palani, A. Tetrahedron Lett., 1993, 34, 3223 H

OH I

5 eq. TABH, AcOH/MeCN

Me

^

,/^S1

-35°C -» +22°C

J

TABH = Me,NHBH(OAc), Williams. D.R.: Osterhout, M.H.; Reddy, J.P. Tetrahedron Lett., 1993, 34, 3271

Ph1

2eq.SmI2,THF-HMPA CHO N=C

Murakami, M.; Kawano, T.; Ito, H.: Ito. Y. J. Org. Chem., 1993, 58, 1458 )H 1. LDA

2. PhCHO

Ph

(80:20, R) Lagu, B.R.; Crane, H.M.; Liotta. D.C. 7. Org. Chem., 1993, 58, 4191 Et2N2Cu(CN)Li2 , THF

O

-78°C -> it

Yamamoto. Y.: Asao, N.; Meguro, M.; Tsukuda, N.; Nemoto, H.; Sadayori, N.; Wilson, J.G.; Nakamura, H. J. Chem. Soc. Chem. Commun., 1993, 1201

254

Compendium of Organic Synthetic Methods, Vol 9

Section 326

H Yb(OTf)3,NHEt2 CH2C12,20 min

«"*/

\ _.

97%

>99% a-attack Chini, M.; Crotti, P.; Favero, L.; Macchia, F.; Pineschi, M. Tetrahedron Lett., 1994, 35, 433 n

EtzNH ? LiBp4 ^ MeCN

80°C, 18h Chini, M.; Crotti. P.: Favero, L.; Macchia, F. Tetrahedron Lett., 1994, 35, 761

Cbz (21

Cbz 79) 52%

:

Naito. T.: Tajiri, K.; Harimoto, T.; Ninomiya, I.; Kiguchi, T. Tetrahedron Lett., 1994, 35, 2205

CH3NO2 ,2 eq. A1C13 80°C, 5h

Sartori. G.: Bigi, F.; Maggi, R.; Tomasini, F. Tetrahedron Lett., 1994, 35, 2393

Ph I

1. Li , cat. 2. PhCHO 3.H20

*•

PhHN'

various electrophiles were used Almena, J.; Foubelo, F.; Yus. M. 7. Org. Chem., 1994, 59, 3210 OH

MeCH=N-OMe , iPrOH

93% (1:1)

Shono. T.: Kise, N.; Fujimoto, T.; Yamanami, A.; Nomura, R. J. Org. Chem., 1994, 59, 1730

Section 326

Alcohol - Amine

255

l.BH 3 'SMe 2 ,THF »f 2. MeOH 3. H2O2, NaOH

i i C4H9 Goralski. C.T.: Hasha, D.L.; Nicholson, L.W.; Zakett, D.; Fisher, G.B.; Singaram. B. Tetrahedron Lett., 1994, 35, 3251

Sm, Me3SiCl/NaI, MeCN

72% Akane, N.; Hatano, T.; Kusui, H.; Nishiyama, Y.; Ishii. Y. J. Org. Chem., 1994, 59, 7902 0

OH

1. NaHMDS , THF 2. PhCHO NBn2

NBn2

(92;8 R:S) 9Q%

withLDA (63:7 R:S) 90% Lagu, B.R.; Liotta. B.C. Tetrahedron Lett., 1994, 35, 4485

l.BMS,THF 2. MeOH 3. H2O2, NaOH x 76% O Goralski. C.T.: Hasha, D.L.; Nicholson, L.W.; Singaram. B. Tetrahedron Lett., 1994, 35, 5165

OH

H

ultrasound, Al(Hg), aq. THF 2h N02 Fitch, R.W.; Luzzio. F.A. Tetrahedron Lett., 1994, 35, 6013

ru

92%

256

Compendium of Organic Synthetic Methods, Vol 9

NHr-Bu

r-BuNH2,CH2Cl2 5% Yb(OT03 , rt, 16h

CH 8 J7

b

Section 326

PH

+

O—'

CgHl

^ XOH

c H

« n

-NHr-Bu

(>99 : <1) 99% Crotti. P.: Favero, L.; Macchia, F.; Pineschi, M. Tetrahedron Lett., 1994, 35, 7089

f"

l.Cp 2 Zr(Bu) 2 ,THF -78°C -» rt,4h

1 ^k O OMe

2. BF3OEt2, THF, 0°C 3. aq. NaOH

82% (>98:2 syn:anti) Ito, H.; Dceuchi, Y.; Taguchi. T.: Hanzawa, Y.; Shiro, M. J. Am. Chem. Soc., 1994, 116, 5469 Na, iPrOH , THF

OH

76% (erythro/threo = 0.8) Bartoli, G.; Cimarelli, C.; Palmieri. G. J. Chem. Soc., Perkin Trans. L, 1994, 537

85%

Booth, S.E.; Benneche, T.; Undheim. K. Tetrahedron, 1995, 51, 3665

MeOzC^

Io

' Ph

PhNH2, TiCl3, PhCHO THF/CH2C12, Py, rt

NHPh

^^v^-"/\

Clerici, A.; Clerici, L.; Porta. O. Tetrahedron Lett., 1995, 36, 5955

HO

Ph

76%

Section 327

Alcohol - Ester

257

BnNH2, lOkbar ,CH2C12

|O

-

I

cat. Yb(OTf)3 , rt, 6d

|

90%

v

^'NHBn Meguro, M.; Asao, N.; Yamamoto. Y. J. Chem. Soc., Perkin Trans. L, 1994, 2597 NHf-Bu O3Os=Nf-Bu, DME, 25°C ,Ph

quinuclidine , 36h (97 Rubinstein, H.; Svendsen, J.S. Acta Chem. Scand. B., 1994, 48, 439

1.TFAA,CH£12 rt,4h ,OH

95%

©O Fontenas, C.; Bejan, E.; Haddon, H.A.; Belavoine. G.G.A. Synth. Commun., 1995, 25, 629

SECTION 327: ALCOHOL, THIOL - ESTER OBn

'OMe

|

3% LiClO4, -30°C h

O$Me2/-Bu

OSiMe2fBu

(92

:

8)

>84%

Reetz. M.T.: Fox, D.N.A. Tetrahedron Lett., 1993, 34, 1119 \

f

f

EtOH , CO, NaBr , iPr2NEt

^^ I

Pd2(C4H7>2Cl2, maleic anhydride

8fi~

Shimizu. I.: Maruyama, T.; Makuta, T.; Yamamoto. A. Tetrahedron Lett., 1993, 34, 2135 \

£)Me

PhCHO,5%SmI 2 ,5min

>=*

ph

^ '^ OTMS

CH2C12,-78°C

Van de Weghe, P.; Collin. J. Tetrahedron Lett., 1993, 34, 3881

"C02Me

258

Compendium of Organic Synthetic Methods, Vd 9

Section 327

9H

Yeast,pet. ether, H2O

it, Id Yeast = Saccharomyces cerevisiae

58% (94% ee)

Jayasinghe, L.Y.; Smallridge. A.J.: Trewhella, M.A. Tetrahedron Lett., 1993, 34, 3949

Mn(OAc)3»2 H2O Cu(OAc)2«H20 25°C Oshima, T.; Sodeoka, M.; Shibasaki, M. Tetrahedron Lett., 1993, 34, 8509 MM™ , n NHC02r-Bu * CO2Me

l.cat.OsO4,TMNO acetone, water 2. 5%aq.HCl

r-BuO2CHN \ *' ^

^o^

-^ *Uli

Panek. J.S.: Zhang, J. J. Org. Chem., 1993, 58, 294 \

OSiMe3 .

PhCHO

^

/

\ JL _ .

._

92%

rOMe

Dicker. I.E. J. Org. Chem., 1993, 58, 2324 ™S OMe

10% [Cp2Zr(Or-Bu)THF][BPh4] CH c

2 l2 . PhCHO , rt , Ih (1.1

:

1) 95%

Hong, Y.; Norris, DJ.; Collins. S. 7. Org. Chem., 1993, 58, 3591 ^^ ^ C02r-Bu

l.LDA 2. Et2AlCl

•" \ 56% - "X^ CO2r-Bu ° (84:16 syn:anti) Tavlor. S.K.: Fried, J.A.; Grassl, Y.N.; Marolewski, A.E.; Pelton, E.A.; Poel, T.-J.; Rezanka, D.S.; Whittaker, M.R. 7. Org. Chem., 1993, 58, 7304 3

Section 327

Alcohol - Ester

259

BrCH2CO2Et, PhTeLi/CeCl3

JL

ether,0°C -> rt

95% Fukuzawa. S.-i.: Hirai, K. J. Chem. Soc., Perkin Trans. L, 1993, 1963

02Et

oxido reductase from Geotrichum candidum

QH 1

^ 500 mM fctf-TRIS-HCl 24h , NaDPH , ADH , glucose

(>99% de; 92% ee) Kawai. Y.: Takanobe, K.; Tsujimoto, M.; Ohno, A. Tetrahedron Lett., 1994, 35, 147 PhCHO

OH

+

OH

O

O

Sn(OTf)2

I II . JL JL ^OPMP _/ Sn(OAc)4 * ' y'^ '^^^OPMP "•" ^ ^ / \ chiral diamine | TBSO OPMP CH2C12,-78°C OTBS OTBS (6 : 94) 95% PMP = p-methoxyphenyl 92%ee Kobavashi. S.: Kawasuji, T. Tetrahedron Lett., 1994, 35, 3329 CHO

3 eq. CH2=CHCO2Me

SnBua

1.2MgBr2,CH2Cl2 0°C, Ih 58% (>20:1 endo:exo)

Woo. S.H. Tetrahedron Lett., 1994, 35, 3975 CH2C12, -78°C PhCHO

QH «~

^^

^uu2tt + Ph'

13%(26%ee) Kivooka. S.: Kido, Y.; Kaneko, Y. Tetrahedron Lett., 1994, 35, 5243

260

Compendium of Organic Synthetic Methods, Vol 9

Section 327

BnOCH2CHO,5%binolTiCl2 toluene, 0°C, 2h

EtS'

EtS 81% (94% ee, R)

Mikami. K.: Matsukawa, S. 7. Am. Chem. Soc., 1994, 116, 4077 MeOH , Amberlyst-15 , 20h 96%

OH

Anand. R.C.: Selvapalam, N. Synth. Commun., 1994, 24, 2743 OH

%1__

1.

CO2iPr Ti(OiPr>4L ,Ti(Oi

O O

CH2C12 , -20°C, 2d 2.iPrOH 3.1M HC1

I

L = chiral imine ligand Hayashi, M.; Inoue, T.; Oguni. N. 7. Chem. Soc. Chem. Commun., 1994, 341 Br

\/co2Et ,THF,2h

/

\ /OH

O

LVT.rt LVT = low valent titanium Aoyagi, Y.; Tanaka, W.; Ohta. A. 7. Chem. Soc. Chem. Commun., 1994, 1225 „. . OMe

l.BuLi, ether, -40°C 2. PhCHO 3.O3,CH2C12)-78°C 4. Me2S 51%

Hormuth, S.; ReiBig. H.-TJ.: Dorsch, D. Liebigs Ann. Chem., 1994, 121 RuBr^chiral bis-phosphine) CO2Me

OH =

60psiH 2 ,aq.MeOH

quant. (99% ee, S) Burk. M.J.: Harper, T.G.P.; Kalberg, C.S. 7. Am. Chem. Soc., 1995, 117, 4423

Section 328

Alcohol - Ether

261

VO(OAc)2, PhH , TBHP

oChoudary, B.M.; Reddy, P.N. Synlett, 1995,959 Also via:

Section 313 (Alcohol - Carboxylic Acid).

SECTION 328:

ALCOHOL, THIOL - ETHER, EPOXIDE, THIOETHER O

1.5NaH,THF,50°C 2. NaOAc , Ac20 , 100°C

(18

:

1) 78%

Mandai. T.: Ueda, M.; Kashiwagi, K.; Kawada, M. Tetrahedron Lett., 1993, 34, I I I

O

1.0.1%[PdCl(7tC3H5)]2 0.2% R-MOP, HSiCl3

H|

40°C, 24h 2. KF, KHCO3 ,

65 x 83% Uozumi, Y.; Havashi. T. Tetrahedron Lett., 1993, 34, 2335

Me2HC

jCHMe2 O

1. BH3-SMe2, Me2S , 0°C 2. aq. NaOH , H2O2 3. NaOH 97% (93% ee)

ClMolander. d.A.: Bobbitt, K.L. J. Am. Chem Soc., 1993, 115, 7517

262

Compendium of Organic Synthetic Methods, Vol 9

Section 328

1. BuCHO , Li(powder)

5% DTBB , THF, 0°C

EtOL

OH

.Cl

^-^

2

l

-H 2 0

v

^

8?%

Guijarro, A.; Yus. M. Tetrahedron Lett., 1993, 34, 3487

TM cat. BF3»OEt2 Mark6, I.E.; Bayston, D.J. Tetrahedron Lett., 1993, 34, 6595

OH ph

2 eq. TMSOTf

Ph •^^

95%

">^

Bartels, B.: Hunter. R. J. Org. Chem., 1993, 58, 6756 Me3Si \

7 PhSH, SiO2 20°C, 20h

Me3Si \

/OH

^PhS^^\

89%

-SPh

I l

14%

Raubo, P.; Wicha. J. Synlett, 1993, 25 ClCH2SPh, SmI2

/

\

\

x°H

/ ^

SPh

73% Yamashita, M.; Kitagawa, K.; Ohhara, T.; lida, Y.; Masumi, A.; Kawasaki, L; Qhta. S. Chem. Lett., 1993, 653

l.PhONa.DMF 2. HC1-H2O

OBn Carlsen. P.H.J.: Aase, K. Acta Chem. Scand. B., 1993, 47,611

Section 328

Alcohol - Ether

Q

rh

263

cat. FeCl3, MeOH, 25°C

V

^

QMe "

™^L

.OH

90%

"

78%

Iranpoor. N.: Salehi, P. Synthesis, 1994, 1152 OH 1. 3 eq. Re2O7 , 9 eq. 2,6-lutidine CH2C12,12h , rt

2. HOONa

*"

I

I

O Boyce, R.S.; Kennedy, R.M. Tetrahedron Lett., 1994, 35, 5133

1. SO(Im)2 OH

2. PhO- Li+

OH 34% °H El Arabi Aouad, M.; El Meslouti, A.; Uzan, R.; Beaupere. D. Tetrahedron Lett., 1994, 35, 6279

)H

PhthNSCl, CHC13 ,60°C, 4d

MeO"

MeO'

^^

^^

64%

precursor to o-thioquinones Capozzi, G.; Menichetti. S.: Nativi. C.: Simonti, M.C. Tetrahedron Lett., 1994, 35, 9451

O OH 73% Marson. C.M.: Harper, S.; Wrigglesworth, R. J. Chem. Soc. Chem. Commun., 1994, 1879

1. r-BuLi, THF , -78°C 2. cyclohexanone 75%

Paquette. L.A.: Dullweber, U.; Branan, B.M. Heterocycles, 1994, 37, 187

264

Compendium of Organic Synthetic Methods, Vol 9

l.Bu3SnCH(OEt)2,BuLi THF, -78°C

PhCHO

Ph.

Section 328

.CH(OEt)2

2. aq. NH4C1 Parrain, J.-L.; Beaudet, I.; Cintrat, J.-C.; Duchene, A.; Ouintard. J.-P. Bull. Soc. Chim. Fr., 1994, 131, 304

(CF£O2)ReO3, 2,6-lutidine, CH2C12

H McDonald. F.E.: Towne, T.B. J. Org. Chem., 1995, 60, 5750

OH PhSeCl, CHC13 SePh (64 Cooper, M.A.; Ward. A.D. Tetrahedron Lett., 1995, 36, 2327

OH 36) quant.

:

O

-OH

2 H

' 2°

Corev. E.J.: Palani, A. Tetrahedron Lett., 1995, 36, 3485

toluene, reflux 3h

66% .; Cho, C.M. Tetrahedron Lett., 1995, 36, 4845

HO

Section 329

Alcohol - Halide

11 n ^O V'^^ L

J

265

1.2% CP2Ti(04-ClC6H4)2, toluene 1% TBAF, A12O3 , 5 PMHS , rt

C5Hn

2.1M NaOH, THF

QL .OH \^ ^^ I

J

PMHS = polymethylhydrosiloxane 94% (70:1) Verdagauer, X.; Berk, S.C.; Buchwald. S.L. J. Am. Chem. Soc., 1995, 117, 12641 BF3OEt2,NaBH3CN

/

7

\X

/ '

6h

\ OH 87%

Srikrishna. A.: Viswajanani, R. Tetrahedron, 1995, 51, 3339 ^

e', MeOH, aq. MeCN, ~

^

_OMe

O

lh

/

'OH

Safavi. A.: Iranpoor. N.: Fotuhi, L. Bull. Chem. Soc. Jpn., 1995, 68, 2591 REVIEW: "Metal-Catalyzed Direct Hydroxy-Epoxidation of Olefins," Adam. W.: Richter, M.J. Accts. Chem. Res., 1994, 27, 57

SECTION 329: ALCOHOL, TfflOL - HALEDE, SULFONATE 1. LDA. ZnCl2 , THF. -78°C 2. PhCHO Cl Mallaiah, K.; Satyanarayana, J.: Ila. H.: Junjappa, H. Tetrahedron Lett., 1993, 34, 3145

EtO£ Baker's yeast

EtO^C \

E )........QH

''""OH

(23 : 77) 74% Tsuboi. S.: Furutani, H.; Ansari, M.H.; Sakai, T.; Utaka, M.; Takeda, A. J. Org. Chem., 1993, 58, 486

266

Compendium of Organic Synthetic Methods, Vol 9

Section 329

1. Dibal, CH£12, -78°C *2. ZnBr 2 , CH2C12,40°C Ishihara. T.: Hayashi, H.; Yamanaka, H. Tetrahedron Lett., 1993, 34, 5777 CF3CO2Et

MgBr 2 , Bu4NBH4

H Ph

ether/CH^

72%

+

"*Ph ^^^^ ^^^^ Ph **** *Q Bailey, P.L.; Briggs, A.D.; Jackson, R.F.W.; Pietruszka, J. Tetrahedron Lett., 1993, 34, 6611 , Bu 4 NBr, 5h CHC13 93%

Suh. Y.-G.: Koo, B.-A.; Ko, J.-A.; Cho, Y.-S. Chem. Lett., 1993, 1907 NaIO4, NaHSO3 90% Masuda, H.; Takase, K.; Nishio, M.; Hasegawa, A.; Nishiyama, Y.: Ishii. Y. J. Org. Chem., 1994, 59, 5550

^£>

v'f

LiCl,DMF,70°C,ld

Cl

OH

I O

(35 : Nymann, K.; Svendsen, J.S. Acta Chem. Scand. B., 1994, 48, 183

PhCHO

'CN

65) 90%

, In !

84% (56:44 erythro:threo) Araki, S.; Yamada, M.: Butsugan. Y. Bull. Chem. Soc. Jpn., 1994, 67, 1126

Section 330

Alcohol - Ketone

267

REVIEW:

"Regioselective anbd Chemoselective Synthesis of Halohydrins by Cleavage of Oxiranes with Metal Halides," Bonini. C.: Righi, G. Synthesis, 1994, 225

SECTION 330: ALCOHOL, THIOL - KETONE O Bu3SnH, AIBN, PhH Ph

syringe pump addn reflux

X^Xt^/ 72% OH (22:1, |5: a) Rawal. V.H.: Krishnamurthy, V.; Fabre, A. Tetrahedron Lett., 1993, 34, 2899 M

15min

Curci, R.; D'Accolti, L.; Detomaso, A.; Fusco, C.; Takeuchi. K.: Ohga, Y.; Eaton. P.E. Tetrahedron Lett., 1993, 34, 4559 OTIPS

PhCHO.MesAl

OTIPS OH

Shoda, H.; Nakamura, T.; Tanino, K.; Kuwajima, I. Tetrahedron Lett., 1993, 34, 6281

1. Me3Si(OTf)2, NEt3 2. PhCHO

I

78% (91:9 syn:anti)

Kobavashi. S.: Nishio, K. 7. Org. Chem., 1993, 58, 2647 )Ac

RuCl 3 , MeCOsH MeCN - H2O - CH2C12

r y

'

\

'

^^s,

78%

'O Murahashi. S.-I.: Saito, T.; Hanaoka, H.; Murakami, Y.; Naota, T.; Kumobayashi, H.; Akutagawa, S. 7. Org. Chem., 1993, 58, 2929

268

Compendium of Organic Synthetic Methods, Vol 9

«

X>XT

Section 330

, acetone X.

^

^

>96%

' OH OH (>n% ee, R) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci. R. J. Org. Chem., 1993, 58, 3600 0°C

l.BuLi,CO,-110°C THF/pentane/ether 2.rt,H 3 0

+

9H I

Ph. »»

/

75%

^—/ H \ O

Seyferth. P.: Hui, R.C.; Wang, W.-L. J. Org. Chem., 1993, 58, 5843 )SiMe3 PhCHO, 5% Sc(OTf)3 , aq. THF

83%

Kohavashi. S.: Hachiya, I.; Ishitani, H.; Araki, M. Synlett, 1993, 472 OTMS ,

9H

, CH2d2

9

PhCHO 2%B(QFs)3

PIT

—

Ph

84%

Ishihara, K.; Hananki, N.; Yamamoto. H. Synlett. 1993, 577 °H

HMPA, rt, THF O

83%(83:17anri;jy/i) Miyoshi, N.; Takeuchi, S.; Ohgo, Y. Chem. Lett., 1993, 959 MeCO3H, cat. OsCl3 MeCN-H20-CH2Cl2 Murahashi. S.-I.: Naota, T.; Hanaoka, H. Chem. Lett., 1993, 1767

O

62%

Section 330

Alcohol - Ketone

OSiMe3

269

PhCHO, A12O3 ultrasound, 22h

(77 Ranu. B.C.: Chakraborty, R. Tetrahedron, 1993, 49, 5333

OH

PhCH2CHO

ph

CHO H2O , SmI2

I OH

(39 : Miyoshi, N.; Takeuchi, S.; Ohgo, Y. Chem. Lett., 1993, 2129

.OTMS PhCHO

9H

, EtCN, -78°C — i20% chiral acyloxyborane 2. aq. HC1

81%(85%ee,R) Ishihara, K.; Maruyama, T.; Mouri, M.; Gao, Q.; Furuta, K.; Yamamoto. H. Bull. Chem. Soc. Jpn., 1993, 66, 3483 1. 2.2 eq. Sml3 , tetrahydropyran 2. propanal

O

95%

Namy. J.-L.: Colomb, M.; Kagan. H.B. Tetrahedron Lett., 1994, 35, 1723 OH

TFA, CDC13 OH

2d

" O

Etechoux. L.: Doris. E. Tetrahedron Lett., 1994, 35, 2017

95:5 (trans:cis)

270

Compendium of Organic Synthetic Methods, Vol 9

Ph

Section 330

C1

3eq.pyridine Araneo, S.; Clerici, A.; Porta. O. Tetrahedron Lett., 1994, 35, 2213

OH

Pt -C1 cat. HZSM-5 DCE, reflux

HZSM-5 = acidic zeolite [SiO2/Al2O3 = 40] Paul, V.; Sudalai, A.; Daniel, T.; Srinivasan. K.V. Tetrahedron Lett., 1994, 35, 2601 l.LDA,THF,-78°C 2. (iPrO^Cl Plr

^^

3. acetone,

\c?

_7goC OH 51% conversion (88% yield)

Adam. W.: Muller, M.; Prechtl, F. J. Org. Chem., 1994, 59, 2358 )H

O

PhCHO, 10% Sm(hmds)3 CsHn

ou^.ioii Cl 90%

Sasai, H.; Arai, S.; Shibasaki. M. J. Org. Chem., 1994, 59, 2661 OSiMe3 PhCHO, Yb(OTf)3 aq. THF, it, 19h

Ph 91% (73:27 syn:anti)

Kohayashi. S.: Hachiya, I. J. Org. Chem., 1994, 59, 3590

Section 330

Alcohol - Ketone

271

£>H

\

1. Me3Al, PhSeH 2.Me2C=CHCH2CHO

<,

V

/

|

>

92%x62%

3. BusSnH, hv

Lee. I.-Y.C.: Lee, J.H.; Lee, H.W. Tetrahedron Lett., 1994, 35, 4173 OH

l.NaHMDS,THF 2. PhCHO NBn2

NBn2

•

(94

NBn2 .

6) 69%

Goh, J.B.; Lagu, B.R.; Wurster, J.; Liotta. D.C. Tetrahedron Lett., 1994, 35, 6029 O

1. LHMDS , toluene-hexane

f-Bu ^^^

^^^.

Bu

2. Y(OTf)3, 0°C,18h

Crotti. P.: Di Bussolo, V.; Favero, L.; Macchia, F.; Pineschi, M. Tetrahedron Lett., 1994, 35, 6537 1. PdCl2[R-BINAP], PhCl2SiSiMe3 , PhH 2. MeLi

ph

3.H30+ 4. HBF4 5. H2O2 Matsumoto, Y.; Havashi. T.: Ito. Y. Tetrahedron, 1994, 50, 335 O

|| O

,Yb(OT03,0°C

PhCHO

QH

0

73x78%

°

OH

, ether, 3h

92% (34:66 threo:erythro) Fukuzawa. S.-i.: Tsuchimoto, T.; Kanai, T. Bull. Chem. Soc. Jpn., 1994, 67, 2221

272

Compendium of Organic Synthetic Methods, Vol 9

Section 330

OTMS OCOzMe

Jl

h

x

SnBu3

—(

----

OCOzMe ft

I JL

Bu4NC104 , c'

PlT"^"^ 94% Yoshida. J.: Morita, Y.; Ishichi, Y.; Isoe. S. Tetrahedron Lett., 1994, 35, 5247

SmI2,PhCH2Br Ph —

HMPA

Enholm. E.J.: Schreier, J.A. J. Org. Chem., 1995, 60, 1110 PhCHO, MS 4A, 13h 5%PdCl2[R-DINAP]-AgOTf

Q

O OH

87% Sodeoka, M.; Ohrai, K.; Shihasaki. M. 7 Org. Chem, 1995, 60, 2648

9%

H

OH

/V? ^O

I Jl

' acetone, it, Id

[

|

-OH \xWQ Bovicelli. P.: Lupattelli, P.; Sanetti, A.; Mincione, E. Tetrahedron Lett., 1995, 36, 3031

Zn(NO3)2, acetone H Me2NCH2CH2OH 30°C, 6h

NO2 pH 10.1 98% 0% pH 11.0 0% 100% Buonora. P.T.: Rosauer, K.G.; Dai, L. Tetrahedron Lett., 1995, 36, 4009

92%

Section 330

Alcohol - Ketone

273

l.B U3 SnH,AIBN,PhH relux 2. PhCHO, 10°C, 12h

73% (6:1 erytrho:threo) Enholm. E.J.: Whitley, P.E. Tetrahedron Lett., 1995, 36, 9157 O

1. SmI2 , Br

^ O^

2.H2O

Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mori. N. Synth. Commun., 1995, 25, 389 Ph

\xXNT«i

DMSO, KSF, microwave, 3 min

A /\ Ph—A)

n If

-

Url

O

55%

Villemin. D.: Hammadi, M. Synth. Commun., 1995, 25, 3141 ,O

1. LDA 2. Ti(OiPr)3Cl

53%

3.TBHP,BaO . ^— OH OH 4. NH4F , ^ Schulz. M.: Kluge, R.; SchuBer, M.; Hoffmann, G. Tetrahedron, 1995, 51, 3175

r

i

OH T

OH I

C13CCO2H , 11°C , C12 ,

O

EtOH,NaHC03 (CH2jT^ Tassignon. P.S.G.: De Wit, D.; De Rijk, T.C.; De Buyck, L.F. Tetrahedron, 1995, 51, 11863

1.2eq.SmI2,-60°C ->-5OC —+* 2. cyclohexanone, -50°C

0oC

f^

O II

I

II

CO2Et

^^^^^^

OH

Utimoto. K.: Matsui, T.; Takai, T.; Matsubara, S. Chem. Lett., 1995, 197

98%

274

Compendium of Organic Synthetic Methods, Vol 9

Ph

I

Section 331

1. AlMe3 Ph

^r

Ph

79% (13:87 erythro:threo)

Aoki, Y.; Oshima. K.: Utimoto. K. Chem. Lett., 1995, 463 .OTMS ,(C6F5)3B,CH2Cl2

OH O I II 99% -78°C , 6.5h Ph^^^^^^ Ph Ishihara, K.; Hanaki, N.; Funawashi, M.; Miyata,M.; Yamamoto. H. Bull. Chem. Soc. Jpn., 1995, 68, 1721 PhCHO

*-

SECTION 331: ALCOHOL, THIOL - NITRILE 3:lEtCN-CH2Cl2,10h 20% Mg-dihydrooxazolidine catalyst OTMS C6H13- CHO »1 12% bis-dihydro oxazolidine p ™ /'^"""""'CN derivative Corev. E.J.: Wang, Z. Tetrahedron Lett., 1993, 34, 4001

gg«^ (95% ee, S)

, 2h, rt

100 units enzyme 0.1M citrate buffer

93% conversion <80%ee>

'^XX^^CN

enzyme = hydroxynitrile lyase from Hevea brasiliensis Klempier, N.; Griengl. H.: Hayn, M. Tetrahedron Lett., 1993, 34, 4769 OH

Me2C(CN)OH , Ih La(OiPr)3 , 50°C

80%

Ohno, H.; Mori, A.; Inoue. S. Chem. Lett., 1993, 975 02

1. LiCH2CN 2. H30+

H 73%

CioH2r Hove. T.R.: Crawford, K.B. J. Org. Chem., 1994, 59, 520

^^

CN

Section 331

^

Alcohol - Nitrile

,

,

o==<

^

>=o

275

1. TMSCN, CH2C12, it KCN/18-crown-6 2.MeOH/THF,SmI2

Olson, S.H.; Danishefskv. S.J. Tetrahedron Lett., 1994, 35, 7901

l.LDA,THF,-78°C

OH I

OH

2. PhCHO Ph Ph (5.5 : 1) 70% Carlier. P.R.: Lo, K.M.; Lo, M.M.-C.; Williams, ID. J. Org. Chem., 1995, 60, 7511

[ LDA, PhCH2CN ], TMSC1

^*^ J^* ^v. -x^

-^^

PhCHO

„..x^ ph

97%

Ph Zhou, J.J.P.; Zhong, B.; Silverman. R.B. 7. Org. Chem., 1995, 60, 2261 HO NH

PhCHO

H

O -Me3SiCN , Ti(OiPr)4

72% (91% ee , S)

Bolm. C.: Muller, P. Tetrahedron Lett., 1995, 36, 1625 H

CHO

ICH2CN , PdCl2/Ga-THF 2 eq. Cl3CCO2Et reflux , lOh

a

c

Zhang, X.-L.; Han, Y.; Tao, W.-T.; Huang. Y.-Z. 7. Chem. Soc., Perkin Trans. L, 1995, 189

Review: "Catalytic Asymmetric Cyanohydrin Synthesis," North. M. Synlett, 1993, 807

276

Compendium of Organic Synthetic Methods, Vol 9

Section 332

SECTION 332: ALCOHOL, THIOL - ALKENE Allylic and benzylic hydroxylation (C=C-C-H -» C=C-C-OH, etc.) is listed in Section 41 (Alcohols from Hydrides).

2MeMgBr,CuCN BF3OEt2, THF

OH

V "

"BnO -78°C

Kang. S-K : Lee, D-H.; Sim, H-S.; Lim, J-S. Tetrahedron Lett., 1993, 34, 91 )TIPS O O

PhCHO Et2

1.TIPSC1 2. MeLi >

II / f

^ TMSI, THF

*•

3 1 Mel V*oT

Q-^^wpt.

47%

OTIPS

72%

81% MeMgBr Tsukazaki, M.; Snieckus. V. Tetrahedron Lett., 1993, 34, 411 Lee, J.; Tsukazaki, M.; Snieckus. V. Tetrahedron Lett., 1993, 34, 415

MeO 2 SmI

2' rt 2 /-BuOH , THF

CHO T :

OH

1) 66%

Gillmann. T. Tetrahedron Lett., 1993, 34, 607 BuLi,THF.-78°C

CsHn ft 5 11 O

QH

Takano. S.: Sugihara, Y.; Ogasawara, K. Tetrahedron Lett., 1993, 34, 845

Cl

H

LxsLi,2iPrCHO 5% DTBB , THF, 0°C * 2. H2O-HC1

(1:1 diastereomers) Guijarro, A.; Yus. M. Tetrahedron Lett., 1993, 34, 2011

OH

71%

Section 332

Alcohol - Alkene

S

277

^- ->w

2.NaOH,H 202

* r£

•

--

^ ^ ^

r.

I

^QH

p^^

13) after 24 h at rt

J.AG,

_

, 25°C, 2h

II

90%

only product (90%)

Singleton. D.A.: Kim, K.; Martinez, J.P. Tetrahedron Lett., 1993, 34, 3071

OH

OH

l.PhCHO,DMF,0°C 2.H20

(3 Kobavashi. S.: Nishio, K. Tetrahedron Lett., 1993, 34, 3453

:

97) 89%

OH 10 eq. BuLi, 10 min

71% OH Lautens. M.: Gajda, C. Tetrahedron Lett., 1993, 34, 4591 Bi

v

Br

/ '

/

Br

CsHTCHO, EG-Zn

OH

DMF, 0°C, 2h

„„ 3

C H

72% EG-Zn = electrogenerated reactive zinc Tokuda. M.: Mimura, N.; Karasawa, T.; Fujita, H.; Suginome. H. Tetrahedron Lett., 1993, 34, 7607 PhCHO , hv (>320 nm) EtCN , -78°C , 5h

Et

(30

°H

.

Takuwa. A.: Shiigi, J.; Nishigaichi, Y. Tetrahedron Lett., 1993, 34, 3457

70) (86:14 E:Z)

278

Compendium of Organic Synthetic Methods, Vol 9

Section 332

Et2Zn , Ti(OiPr)4 ,12h -60°C -> -55°C

CHO

8%

J»»» /"v~""z

k

Ef

(93% ee) Tf Rozema, M.J.; Eisenberg, C.; Liitjens, H.; Ostwald, R.; Belyk, K.; Knochel. P. Tetrahedron Lett., 1993, 34, 3115

1,2-dichlorobenzene, 12h reflux, <0.5 torr ""V.

H

OH

^ ^**.

90%

^

OH Janardhanam, S.; Devan, B.; Rajognpalan. K. Tetrahedron Lett., 1993, 34, 6761

1. Sharpless epoxidation 2. TsCl ,

Ph

3. Te, LiBHEt3, THF TBAF,rt

^

78%(>90%ee)

Dittmer. D.C.: Discordia, R.P.; Zhang, Y.; Murphy, C.K.; Kumar, A.; Pepito, A.S.; Wang, Y. J. Org. Chem., 1993, 58, 718 iPrMgBr,THF u

(tbp)2Ni2C!2

Bu \

K

Bu

(CH2)2CH2OH

(CH2)2CH2OH

(>25 1) 60 : Ducoux, J.-P.; LeMenez, P.; Kunesch. N.: Wenkert. E. .7. Org. Chem., 1993, 58, 1290

Me3SiSnBu3, DMF CsF,rt,lh

I

,^ //

OH Mori. M.: Isono, N.; Kaneta, N.; Shibasaki, M. J. Org. Chem., 1993, 58, 2972

86%

Section 332

Alcohol - Alkene

279

hv, CO, THF, 8h

Merlic. C.A.: Xu, D.; Gladstone, B.C. 7. Org. Chem., 1993, 58, 538

.H

O

EtMgBr, 10% Zr complex THF,25°C

> 65% (>97% ee) HO Morken, J.P.; Didiuk, M.T.; Hovevda. A.H. 7. Am. Chem. Soc., 1993, 115, 6997

TMS OH OTMS

5% (binol)TiC!2 , BnO2C—CHO

Me 63% (99:1 syn:anti; 99:1 Z:E; 99% ee, R) Mikami. K.: Matsukawa, S. 7. Am. Chem. Soc., 1993, 115, 7039

SiMe3 >EtCN 20% chiral ligand PhCHO

2. TBAF

| 63% (92%ee)(96:4 erythro:threo) OH Ishihara, K.; Mouri, M.; Gao, Q.; Maruyama, T.; Furuta, K.; Yamamoto. H. 7. Am. Chem. Soc., 1993, 115, 11490

1

,10% Pd(OAc)2

2 NaO2CH , 2 BU4NC1, 2 iPr2NEt Me2NCOMe,80°C,ld I Larock. R C : Ding, S.; Tu, C. Syntett, 7PP3, 145

|l

70%

(56:44£:Z)

280

Compendium of Organic Synthetic Methods, Vol 9

Ph

•YoSc'.M?

-

Section 332

^

^"

2.H 2 O 2 ,NaOH

X =

—]

Singleton. D.A.: Redman, A.M. Tetrahedron Lett., 1994, 35, 509

ry/ _ '

(Ipc)2B

SiMe^h

Buvnak. J.D.: Geng, B.; Uang, S.; Strickland, J.B. Tetrahedron Lett., 1994, 35, 985 t

Bi

rf"»_

r-f _/"» T\J~M

X~1T T

f~*t

2. Me2Zn 3.PhCHO,0°C 94%

Wipf. P.: Xu, W. Tetrahedron Lett., 1994, 35, 5197 2eq.Me2S=CH2 ,THF

-10°C ^

rt

8Q%

OH

Alcaraz, L.; Harnett, J.J.; Mioskowski, C.; Martel, J.P.; Le Gall, T.; Shin, D.-S.; Falck, J.R. Tetrahedron Lett., 1994, 35, 5449

/~\

iPrMgCl, THF, -50°C 2. PhCHO , -50°C -» -20°C (1.44

:

Szymoniak, J.; Felix, D.; Moi'se. C. Tetrahedron Lett., 1994, 35, 8613

1. HSiCl3 , cat Pd(PPh3)4

~O

1 p,^.^^ ^^,n*-» ™-rr?

n

^"

'

Ph

87% (>99:1 syn:anti)

Kohavashi. S.: Nishio, K. Synthesis, 1994, 457

Section 332

PIT

.^

Alcohol - Alkene

281

Toluene, reflux, 3h "^

-^

"^

I

^~

"^^

^" ~

'

^^^Jl

) -"

Me Ph

73%

(3:2 syn:anti)

Kim. S.: Cho, CM. Tetrahedron Lett., 1994, 35, 8405 Pd(OAc)2 , 3 PPh3 , PhH

XNV

70-C,16h

\-/ ^ 47% Watanabe, T.; Sakai, M.; Miyaura, N.; Suzuki. A. J. Chem. Soc. Ctem. Commun., 1994, 467 CH

°

OH

Xin

BuMgBr

I

X Ss x

C?Hi4' ^ * ^^ N-NHTs Chandrasekhaf. S.: Takhi, M.; Yadav, J.S. Tetrahedron Lett., 1995, 36, 307

1. Li, NH3 , THF—EtOH , -78°C 2. TBAF, THF 3. 30% aq. H2O2, KHCO3 , MeOH '///SiMe2Ph

T ^T

^^

"OH

60% overall

Taber. P.P.: Yet, L.; Bhamidipati, R.S. Tetrahedron Lett., 1995, 36, 351

MPM(X

A/

^.

5% Pd2(dba)3«CHCl3, THF 20%PPh 3l heat MPM(

9H

93% Kang. S.-K.: Park, D.-C.; Park, C.-H.; Hong, R.-K. Tetrahedron Lett., 1995, 36, 405 PhS

/

OH

l.Cp2TiCl 2 /2BuLi,0°C,THF

(97

OH

5

:

3) 69%

Takeda. T.: Miura, I.; Horikawa, Y.; Fujiwara, T. Tetrahedron Lett., 1995, 36, 1495

282

Compendium of Organic Synthetic Methods, Vol 9

Section 332

1. Co(tdcpp), O2-Et3SiH , Ih 2. (MeO)3P, iPrOH,

C3H7' Co(tdcpp) = t5,10,15,20-tetrakis(2,6-dichlorophenyl) porphinato] Cobalt (II) Matsushita. Y.: Sugamoto, K.; Nakama, T.; Sakamoto, T.; Matsui, T.; Nakayama, M. Tetrahedron Lett., 1995, 36, 1879 Ph OBn

3 f-BuOK, BuLi THF, -78°C

RQ

R = TBS (79 : R=H (20 : Tomooka, K.; Keong, P.-H.; Nakai. T. Tetrahedron Lett., 1995, 36, 2789

21) 48% 80) 90%

1. BuLi, THF, -78°C 2. PhCHO,-78°C -> rt

>

f 85%

Mo, X.-S.; Huang. Y.-Z. Tetrahedron Lett., 1995, 36, 3589 ^OMe OMe

OMe

Dibal, 14% Ni(cod)2 20% R-BINAP, Ih iT

IT

78% (97% ee) Lautens. M.: Chiu, P.; Ma, S.; Rovis, T. /. Am. Chem. Soc., 1995, 117, 532

OMe

Section 335

Aldehyde - Amide

283

H Ph1

SnCl4-NBu3, MeCN ^ ^ 65% Yamaguchi. M.: Hayashi, A.; Hirama, M. /. Am. Chem. Soc., 1995, 117, 1151

2eq.HCO2NH4,THF 5% Pd(PPh3)4, reflux linOs..

^r- """«•//"YLT

Rang. S.-K.: Park, D.-C.; Rho, H.-S.; Yu, C.-M.; Hong. J.-H. Synth. Commun., 1995, 25, 203 OMe

, 10% Ti(OiPr)4 PhCHO

• *20% chiral binaphthylamine

Ph

9H II li II 93%(66%ee) ^^^^ OMe

Benisford. D.J.: Bolm. C. Anqew. Chem. Int. Ed. Engl., 1995, 34, 1717

Also via:

Section 302 (Alkyne - Alcohol).

SECTION 333: ALDEHYDE - ALDEHYDE NO ADDITIONAL EXAMPLES SECTION 334: ALDEHYDE - AMIDE

CO (1 atm), Ph2MeSiH 1% Pd(OAc)2,20% PPh3

^X^ --t

CHO

N^ toluene, 110°C, Et4NCl I ^ \ S °>Ph \02Ph Brown, S.; Clarkson, S.; Grigg. R.: Sridharan, V. J. Chem. Soc. Chem. Commun., 1995, 1135

SECTION 335: ALDEHYDE - AMINE IHAc DMF, POC13

Balasundaram, B.; Venugopal, M.; Permumal. P.T. Tetrahedron Lett., 1993, 34, 4249

284

Compendium of Organic Synthetic Methods, Vol 9

Section 341

SECTION 336: ALDEHYDE - ESTER NO ADDITIONAL EXAMPLES SECTION 337: ALDEHYDE - ETHER, EPOXIDE, TfflOETHER

10 eq. PPh3 , CO, H2

"*"

\

/

"CHO + HC(OEt)3,2d (96 + HC(OEt)3 + PPTS, 12h (0 Fernandez, E.; Castilldn. S. Tetrahedron Lett., 1994, 35, 2361 2% Pd(PPh3)4, 5 atm CO, THF \N

EtO 4) quant. 100) quant.

:

C5Hj i

v

>=CHCHO / 82% (13:87 E:Z) Qgawa. A.: Takeba, M.; Kawakami, J.; Ryu, I.; Kambe, N.; Sonoda. N. J. Am. Chem. Soc., 1995, 117, 7564 PhSH, 70°C, 16h

*"

SECTION 338: ALDEHYDE - HALIDE, SULFONATE NO ADDITIONAL EXAMPLES SECTION 339: ALDEHYDE - KETONE NO ADDITIONAL EXAMPLES

SECTION 340: ALDEHYDE - NITRILE NO ADDITIONAL EXAMPLES SECTION 341: ALDEHYDE - ALKENE For the oxidation of allylic alcohols to alkene aldehydes, also see Section 48 (Aldehydes from Alcohols). . Cp2Zr(Cl)CH=CHOEt /~\ cat.AgC104 / V— CHO \ _/ 2.H3O+ Maeta, H.; Suzuki. K. Tetrahedron Lett., 1993, 34, 341 _

Section 341

Aldehyde - ADcene

Ph

CHO

^

285

J^

^

A.

^CHO

2. IN HC1,0«C 75% Duhamel. L.: Duhamel, P.; Le Gallic, Y. Tetrahedron Lett., 1993, 34, 319

"OTMS

a

OTMS

CAN, MeCN, 0°C

Paolobelli, A.B.; Latini, D.; Ruzziconi. R. Tetrahedron Lett., 1993, 34, 721

:HO 25% polymeric Fe catalyst Saha, A.K.; Hossain. M.M. Tetrahedron Lett., 1993, 34, 3833

?9%

cyclic B catalyst , -78°C , 8h

(99:1 ew.endo) , 92% ee Corev. E.J.: Loh, T.-P. Tetrahedron Lett., 1993, 34, 3979

l

PhCHO

—

Me3Si CsF-DMSO,rt^ 100°C

2.Zna 2 ,rt,2h Bellassoued. M.: Salemkour, M. Tetrahedron Lett., 1993, 34, 5281 PhCHO, 5% TfSiMe3 CH 2 Cl 2 ,rt,15h Me3Si OSiMe3 CHO Duhamel. L.: Gralek, J.; Bouyanzer, A. Tetrahedron Lett., 1993, 34, 7745

286

Compendium of Organic Synthetic Methods, Vol 9

N-f-Bu

PnCHO, 10% ZnBr2, THF

(Me3Si)2HC v Bellassoued. M.: Majidi, A. J. Org. Chem., 1993, 58, 2517 f

.CHO

Section 341

.CHO ** Pti//^£3/^

86%

C 8 Hi 7 Br,AIBN

20 atm. CO, PhH, 80°C, 8h

o

CHO

74% Rvu. I.: Yamazaki, H.; Ogawa, A.; Kambe, N.; Sonoda. N. J. Am. Chem. Soc., 1993, 115, 1187

, acetone 2. PH3P=CHCHO, CH2C12 Adger, B.J.; Barrett, C.; Brennan, J.; McGuigan, P.; McKervey. M.A. J. Chem. Soc. Chem. Commun., 1993, 1220

:HO , SmI2,25°C

"CHO (95:5 [1,4:1,3]) 72% Van de Weghe, P.; Collin. J. Tetrahedron Lett., 1994, 35, 2545 SBu

l.Bu3SH,TiCl 4 ,CH 2 Cl 2

\xVx ^

2. POC13, DMF, 0-5°C

CHO

Asokan. C.V.: Mathews, A. Tetrahedron Lett., 1994, 35, 2585 OH

,H20,90°C

||

CHO

I], Ih

75 : 25) 85% D6rien, S.; Dixneuf. P.H. J. Chem. Soc. Chem. Commun., 1994, 2551

67%

Section 342

Amide - Amide

287

Pd(pph3)4, 'OH

O 2 , heat G6mez-Bengoa, E.; Noheda, P.; Echavarren, A.M. Tetrahedron Lett., 1994, 35, 7097 EtO

SnBu3

PhCHO BF3OEt2, CH2C12, -78°C , Ih Cabezas, J.A.; Oehlschlager. A.C. Tetrahedron Lett., 1995, 36, 5127 MnO 2 , hexane, 15 min

,OH

Shinada, T.; Yoshihara. K. Tetrahedron Lett., 1995, 36, 6701 HO

CHO

Ru (indene)Cl(PPh3)2

Ph

Trost. B.M.: Livingston, R.C. J. Am. Chem. Soc., 1995, 117, 9586 CHO

2% [ Rh(CO)2(acac) ] C3H7

==2.2% biaryloxyl phophite

Q jj

85% Johnson, J.R.; Cuny, G.D.; Buchwald. S.L. An%ew. Chem. Int. Ed. Engl., 1995, 34, 1760

Also via |3-Hydroxy aldehydes: Section 324 (Alcohols - Aldehyde). SECTION 342: AMIDE - AMIDE NO ADDITIONAL EXAMPLES Also via Dicarboxylic Acids: Diamines

Section 312 (Carboxylic Acid - Carboxylic Acid) Section 350 (Amines - Amines)

288

Compendium of Organic Synthetic Methods, Vol 9

Section 343

SECTION 343: AMIDE - AMINE J-OH C=N

Ac

d. Ac2O, HC1

100-130°C, 4h Me Viin. R.J.: Arts, H.J.; Maas, P.J.; Castelijns, A.M. 7. Org. Chem., 1993, 58, 887 l.TMSCl,NaI,I 2 TMEDA, MeCN 2. NH3 , 100°C 3. racemization-resolution O

„ 95x77x80%

Armstrong in. I.E.: Eng. K K.: Keller, J.L.; Purick, R.M.; Hartner Jr., F.W.; Choi, W.-B.; Askin, D.; Volante, R.P. Tetrahedron Lett., 1994, 35, 3239 TsHN Pd(OAc>2 , Et2NH 1 atm CO , THF

\ NEt2 (86 : Andersson. P.G.: Aranyos, A. Tetrahedron Lett., 1994, 35, 4441

14) 72%

Me

-70°C -> -20°C *•

OZnCl

Y

-

OMe

Ph

^N xyf^n^

Me0

'

*

58%

N,

Me van Maanen, H.L.; Kleijn, H.; Jastrezebski, T.B.H.: van Koten. G. Reel. Trav. Chim. Pays-Bas, 1994, 113, 567

Section 344

Amide - Ester

Ts I

NHTs

BnNH2,10% Yb(OTf)3

/v

CH 2 Cl 2 ,rt,10h

289

"^X

NHBn

.NHBn

+

J^

NHTs

(>99 : 1) 75% Meguro, M.; Asao, N.; Yamamoto, Y'.-Tetrahedron Lett., 1994, 35, 7395

r-BuNH 2 , NEt3 I

CH2C12, reflux, Id

N^'^O

78%

I

Cl NHr-Bu Chen, P.; Suh, D.-J.; Smith. M.B. J. Chem. Soc., Perkin Trans. 1., 1995, 1317

SECTION 344: AMIDE - ESTER r-BuBr, K£O3 , DMAC BTEAC, 55°C

92%

DMAC = dimethyl acetamide BTEAC = BnEt3NCl Chevallet, P.; Garroust, P.; Malawska, B.; Martinez. J. Tetrahedron Lett., 1993, 34, 7409 IC^Me Mn(OAc)3, CH2(CO2Me)2 •N

Chuang. C.-R: Wang, S.-F. Tetrahedron Lett., 1994, 35, 1283

Si(OEt)4,0.1CsF Ahn. K H.: Lee, S.J. Tetrahedron Lett., 1994, 35, 1875

290

Compendium of Organic Synthetic Methods, Vol 9

Cp 1.15%ZnCl2 , f—Fe,^/^ /-ITT r
Ps.

N

Section 345

S

UL

N •I

2. CAN, MeCN, CO Ph Chen, T.; Jiang, S.; Turos. E. Tetrahedron Lett., 1994, 35, 8325 CO2Me C1

Ph'

| ,N^ -"•

Phv

yCO2Me

Bu3SnH , AffiN , PhH Bn

O

Bn

O

52% GoodaU, K.; Parsons. A.F. 7. Chem. Soc., Perkin Trans. 1., 1994, 3257

CC^Me

1. Sn(OTf)2 CH2C12 ~

CO2Et

78% Nagasaka. T.: Nishida, S.; Sugihara, S.; Kawahara, T.; Adachi, K.; Hamaguchi, F. Heterocycles, 1994, 39, 171

Related Methods:

Section 315 (Carboxylic Acid - Amide) Section 316 (Carboxylic Acid - Amine) Section 351 (Amine - Ester)

SECTION 345: AMIDE - ETHER, EPOXIDE, THIOETHER CO/H2 (1600 psi) ,100°C HC(OEt)3,24h HRh(CO)(PPh)3

\^~ ^( 42% / \ O OEt (2:1 synianti) Eguchi, M.; Zeng, Q.; Korda, A.; Oiioma. I. Tetrahedron Lett., 1993, 34, 915

Section 345

Amide - Ether

291

Ph

,B-O H O

, BH 3 , THF

2. H+ , EtOH

Bn Bn 73% Romagnoli, R.; Roos, E.G.; Hiemstra. H.: Mollenaar, M.H.; Speckamp. W.N.: Kaptein, B.; Schoemaker, H.E. Tetrahedron Lett., 1994, 35, 1087

,O 'Ar

2 Ar'-SH , CH2C12, 0°C L-W-DIPT-Et^n

AT = 4-nitrophenyl; Ar1 = 4-r-butylphenyl

95%

%

Hayashi, M.; Ono, K.; Hoshimi, H.; Qguni. N. J. Chem. Soc. Chem. Commun., 1994, 2699

cyclohexanone, H2SO4 CN

AcOH , Ac20,10°C , Ih

Stambach. J.-F.: Jung, L.; Hug, R. Heterocycles, 1994, 38, 297

10

^Sp-Tol

>*

°

NHBn

cat ZnCl2, CH2C12, 50°C, 6d

J— N

O

54% (80% ee)

Bn

asymmetric Pummerer rearrangement Kita. Y.: Shibata, N.; Kawano, N.; Tohjo, T.; Fujimori, C.; Matsumoto, K. Tetrahedron Lett., 1995, 36, 115

292

Compendium of Organic Synthetic Methods, Vol 9

Section 346

Ph

COzMe

O

1.5 NMO , CH2C12

CO2Me

O Ph O Andres, C.J.; Spetseris, N.; Norton, J.R.; Mevers. A.I. Tetrahedron Lett., 1995, 36, 1613

SECTION 346: AMIDE - HALIDE, SULFONATE

Bn |

CuCl, cat. bipy

O

Bn Nagashima, H.; Ozaki, N.; Ishii, M.; Seki, K.; Washiyama, M.; Itoh, K. J. Org. Chem., 1993, 55,464

PhS. Et3N-3 HF, MeCN

77%

0 Narizuka, S.; Fuchigami. T. J. Org. Chem., 1993, 58, 4200 9H /

Ph^eCO^OAc, I2 hv ,6.5h =0

I

n

*• ^^x

I

>=0

76% Dorta, R.L.; Francisco, C.G.; Suarez. E. Tetrahedron Lett., 1994, 35, 1083

1. [/?-AnP(S)S]2,PhMe,100°C 2. BU4NH2F3 , NIS , CH2C12 rt

F

F

Fs

98x64% Kuroboshi. M.: Hivama. T. Tetrahedron Lett., 1994, 35, 3983

Section 347

Amide - Ketone

293

C3H7

(>99 : 1) 80% Cardillo. G.: Di Martino, E.; Gentilucci, L.; Tomasini. C.: Tomasoni, L. Tetrahedron Asymmetry, 1995, 6, 1957

SECTION 347: AMIDE - KETONE

O

2 DMP, 4 Py , Ih

CH 2 Cl 2 ,rt

^

>• Dess-Martin periodinane

I

J

^N^ O i H ^s^ ^Ji^

^Ph

7
Ph

DMP = l,l,l-triacetoxy-l,r-dihydro-l,2-benzodoxol-3(lH)-one Batchelor, M.J.; Gillespie, R.J.; Golec. J.M.C.: Hedgecock, C.J.R. Tetrahedron Lett., 1993, 34, 167

30% H2O2, Pd(OAc)2 CH 2 Cl 2 ,rt,2h 73%

H Naota, T.; Sasao, S.; Tanaka, K.; Yamamoto, H.; Murahashi. S. Tetrahedron Lett., 1993, 34, 4843 yOEt

TFA, 20°C, Id

OI O Gesson. J.-P.: Jacquesy, J.-C.; Rambaud, D. Tetrahedron, 1993, 49, 2239

47%

294

Compendium of Organic Synthetic Methods, Vol 9

Section 347

, AIBN, PhH (syringe pump addition) 'N ,Br

Beckwith. A.L.J.: Joseph, S.P.; Mayadunne, R.T.A. J. Org. Chem., 1993, 58, 4198

O

O

O

1.3 Mn(OAc)3 2. H30+

^

b*

:, Bouzide, A.; Leblanc, C. Synlett, 1993, 202 TMS

. NMeCO2Me

Me3SiOTf, NEt3

NMeCC^Me

0°C , In

Rossi, L.; Pecunioso. A. Tetrahedron Lett., 1994, 35, 5285

Me

l.BuLi,THF,0°C 2.(C02Et)2

r'Me

.0

3. 12NHC1-DME, reflux 'NHC02f-Bu

'

"\ H

80x88%

Hewawasam. P.: Meanwell, N.A. Tetrahedron Lett., 1994, 35, 7303 .0

/

,p / 70% CH 2 Cl 2 ,rt,2d ^- ' NHCC^Et ten Hoeve, W.; Wynberg, H. Synth. Commun., 1994, 24, 899

PhCH=NCO2Et, BF3OEt2

/ -•( ^ / \

Section 347

Amide - Ketone

>

295

l.MeNHOH

N-Me

JL

K^ 3. H2O via hetero Cope Lantos, I.; Zhang, W.-Y. Tetrahedron Lett., 1994, 35, 5977

Me Si(iPr)3

i. RCOCl 2. MeMgX 3. oxalic acid 4. TFA, CHC13 , heat

^X V 78x86% CO?R

R = (-)-8-phenylmenthyl Comins. D.L.: LaMunyon, D.H. Tetrahedron Lett., 1994, 35, 7343

1. r-BuLi, TMEDA, -78°C NiPr2

< a. 80%

Brenstrum, T.J.; Brimble. M.A.: Stevenson, RJ. Tetrahedron, 1994, 50, 4897

O2N—^ Ph

\

—CHO

CoCl2, MeCN, AcCl

Bhatia, B.; Reddy, M.M.; Iqbal. J. J. Chem. Soc. Chem. Commun., 1994, 713

N2 NHMe

.0

II 0

^ — 4 eq. DMAP, toluene, reflux

(

It II jj

., /Me N \ //

95% Cossv. J.: Belotti, D.; Bouzide, A.; Thelland, A. Bull. Soc. Chim. Fr., 1994, 131, 723

296

Compendium of Organic Synthetic Methods, Vol 9

l.e', AcOH.heat 2. MeOH, Na2CO3

Section 349

r

75x95%

Matsumiira. Y.: Takeshima, Y.-i.; Okita, H. Bull. Chem. Soc. Jpn., 1994, 67, 304

iPrCHO , AcCl, O2 , CoCl2 MeCN ^^ 'NHAc

Reddy, M.M.; Bhatia, B.; Iqbal. J. Tetrahedron Lett., 1995, 36, 4877 O

.N-

Me Podlech, J.: Seehach. D. Helv. Chim. Acta, 1995, 78, 1238

Me

SECTION 348: AMIDE - NITRILE O

-xc

, r-BuOK ph

DMSO, O2

tL

JL

.CN

Ph'

^>^

~ Ph

Jain, R.; Roschangar, F.; Ciufolini. M.A. Tetrahedron Lett., 1995, 36, 3307 SECTION 349: AMIDE - ALKENE

O

\

J ,CH2C12,-50°C ^ ^ +

chiralfcw-sulfoxide,Pels

" O' (6

:

Khiar. N.: Fernandez, I.; Alcudia, F. Tetrahedron Lett., 1993, 34, 111

4)

78%

Section 349

Amide - Alkene

297

l.LDA,THF,-78°C ?h

Is*

I

2.PhCHO,THF

--

-.-

•

reflux Me O Me Ph Couture. A.: Deniau, E.; Grandclaudon, P. Tetrahedron Lett., 1993, 34, 1479

II ¥

\ p

I

, MS4A, CH2C12

20% chiral Yb triflate, 0°C

*——/

S/

T™

"\

I

(89:1 endo:exo; 95%ee) Kohavashi. S.: Hachiya, I.; Ishitani, H.; Araki, M. Tetrahedron Lett., 1993, 34, 4535 4% Pd2(dba)3«CHa3 9.6% RS-BPPFOH silver-exchanged zeolite

Y

i

i

/

DMRDMSO, 0°C, 5d

0 (1

O

:

0 1.4) 94% (86%ee)

Nukui, S.; Sodeoka, M.; Shibasaki. M. Tetrahedron Lett., 1993, 34, 4965

Bl

^

N=

O

^\

,PPh3.THF

^

^*^\

>

p73%

OEt OEt

2% Pd2(dba)3-CHCl3 2eq.iPr2NEt

Torii. S.: Okumoto, H.; Sadakane, M.; Hai, A.K.M.A.; Tanaka, H. Tetrahedron Lett., 1993, 34, 6553

(>97:3 endoiew) Evans. D.A.: Lectka, T.; Miller, S.J. Tetrahedron Lett., 1993, 34, 7027

12%

298

Compendium of Organic Synthetic Methods, Vol 9

Section 349

1.0.2eq.fe(acac)3 3 eq. EtsAl/L 2. ethylene glycol cat. p-TsOH

BzO

(>20 : Takacs. J.M.: Weidner, J.J.; Takacs, B.E. Tetrahedron Lett., 1993, 34, 6219

1) 45%

0.02 PdCl2, 2 eq. CuCL2 3 eq. ClCH2CO2-Na+

Ts ° ° Kimura, M.; Saeki, N.; Uchida, S.; Harayama, H.; Tanaka, S.; Fugami, K.; Tamaru. Y. Tetrahedron Lett., 1993, 34, 7611 1. EtC^C-^N-CC^Et, SnCLt CH 2 Cl 2 ,-60°C,5min 2. Li, NH3 , -33°C 3.10NHC1 87x86% (11:1 E:Z) Brimble, M.A.; Heathcock. C.H. J. Org. Chem., 1993, 58, 5261

Pd(OAc)2, P(o-Tol)3, DMF . BU4NC1,65°C, 40h sealed tube (in vacua)

-NHTs (4 : 1) 78% Harris Jr., G.D.; Herr, R.J.; Weinreb. S.M. J. Org. Chem., 1993, 58, 5452

Section 349

Amide - Alkene

299

Pd(PPh3)4 , PhMe ,100°C

•

Trost. B M : Marrs, C.M. J. Am. Chem. Soc., 1993, 115, 6636 J

_ f

n

Ph3P=CHC02Et toluene , reflux , 4h

O' Boc "^ Boc Baldwin. I.E.: Edwards, A.J.; Farthing, C.N.; Russell, A.T. Synlett, 1993, 49

LNaH.THF.BuLi

2

/

V

.CO2Me

-

3. toluene , Amberlyst 15 , reflux

>96%(>20:1 E:Z)

Lvgo. B. Synlett, 1993, 764

1.2eq.LDA PhCH2002Et 2. PhCH=NPh this reaction forms a p-lactam with 1 eq. of LDA Manhas. M.S.: Chaudhary, A.G.; Raju, V.S.; Robbi, E.W.; Bose, A.K. Heterocycles, 1993, 35, 635

h,^ Q, 1. xylenes , reflux Ph VX°V. 2.PPTS NaH.DMF

N

J^ THPCJ^

L N^

^^^ 68x75% De la Torre, J.A.; Fernandez, M.; Morgans Jr.. P.: Smith, D.B.; Talamas, F.X.; Trejo, A. Tetrahedron Lett., 1994, 35, 15

Zn THF rt lh

' ' ' " NHCO.Me Kise. N.: Yamazaki, H.; Mabuchi, T.; Shono, T. Tetrahedron Lett., 1994, 35, 1561

90%

300

Compendium of Organic Synthetic Methods, Vol 9

Section 349

T!

Ts |

0.1 [Rh(CO)2(acac), dppb AcOH,70°C,6h

I

79%

Oppolzer. W.: Fiirstoer, A. Helv. Chim. Acta, 1993, 76, 2329 1. piperidine, CFaCOjAg

SPh

O

THF, rt

2. C9HiJA&Br, THF NiCl2(dppe), 0°C -» rt

57x60% Babudri, F.; Fiandanese. V.: Naso, F.; Punzi, A. Tetrahedron Lett., 1994, 35, 2067 PhMe2CCH=Mo-N[2,6-(iPr)2C6Hi3] [OCMe(CF3)2]2 N'

"O

PhH.rt ^

J

80-90%

Martin. S.F.: Liao, Y.; Chen, H.-J.; PStzel, M.; Ramser, M.N. Tetrahedron Lett., 1994, 35, 6005 ^SPh l.MeLi 2.NaH SPh

Me'

©PPh3 Burley, I.; Hewson. A.T. Tetrahedron Lett., 1994, 35, 7099

>' | 67% SO2Ph

1. Dibal, toluene, -78°C 3. PCC , 25°C CO2r-Bu 52%(90:10£:Z) Wei, Z.Y.; Knaus. E.E. Synlett. 1994, 345

Section 349

Amide - Alkene

-o N

301

Me

\ / ,MS4A,CH£1 2 20% Yb-BINOL complex

(89 95% ee Kohavashi. S : Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett., 1994, 35, 6325

1 \

/

1 Me«»/v ,BF 3 «OEt 2 ,PhH, reflux H

2. CH2=CHCO2CO2, THF, reflux M Pti

76% (97:3) Barta, N.S.; Erode, A.; Slille. J.R. J. Am. Chem. Soc., 1994, 116, 6201 AT NH2 H2CO, [Rh(OAc)2]2, PPh3, PhH

I 40% H Campi, E.M.; Chong, J.M.; Jackson. W.R.: Van Der School, M. Tetrahedron, 1994, 50, 2533

NHTs Ag3PO4, 5% Pd(QAc)2 I

CgHn

fos-oxazoline catalyst 90°C , Id, DMF 94% (82% ee)

Larock. R.C.: Zenner, J.M. J. Org. Chem., 1995, 60, 482

302

Compendium of Organic Synthetic Methods, Vol 9

/==

Section 349

Ph-N=C=0,AlCl3,40°C

*. Me „ „ CH2Cl2,12h O Niestroi. M.: Neumann, W.P.; Thies, O. Chem. Ber., 1994, 127, 1131 / Me

\

SnMe3

Bu^NF, 66°C 0=C

V

^

50% (4.9:1 E:Z)

7 V ^^\..x^^

50%

NHBn

Bn Jacobi. P.A.: Brielmann, H.L.; Hauck, S.I. Tetrahedron Lett., 1995, 36, 1193 Bu /

5% Cl2Pd(PPh3)2, MeOH, 65°C AcHN

'

i

CO (1 atm), 4 NEt3

N

Ac

78%

Cop6ret, C.; Sugihara, T.; Negishi. E. Tetrahedron Lett., 1995, 36, 1771

TePh

TsNNaCl, EtOH , 20h — NHTs

OH 84% 9 Nishibayashi, Y.; Srivastava, S.K.; Ohe, K.: Uemura. S. Tetrahedron Lett., 1995, 36, 6725 1. LiHMDS , THF, HMPA, -78°C 2. PhNTf2 , -78°C ^ 25°C

94x69% N

Ph

3. Ph^CuLi, THF-HMPA I -78°C -> 25°C I Bz Bz Tsushima, K.; Hirade, T.; Hasegawa, H.: Murai. A. Chem. Lett., 1995, 801

Mi 0.1 AgNCO , 0.1 NEt3 , PhH 50°C, 5h NHTs

\ ~~

'

O Kimura, M.; Tanaka, S.; Tamaru. Y. Bull. Chem. Soc. Jpn., 1995, 68, 1689

98%

Section 350

Amine - Amine

303

Also via Alkenyl Acids: Section 322 (Carboxylic Acid -Alkene) SECTION 350: AMINE - AMINE

ph

Ph

N^ ff

In , aq. EtOH, 16h ^ NH4C1

I I NHPh

quant.

Kalvanam. N.: Rao, G.V. Tetrahedron Lett., 1993, 34, 1647

l.m-cpba,CH 2 Cl 2 0°C -> 25°C

2. H2 (1 atm) , Pd/C MeOH , 15h , 25°C

H

42%

Plaauevent. J.-C.: Chichaoui, I. Tetrahedron Lett., 1993, 34, 5287 PhCN quant.

Ph Rousselet, G.; Capdevielle. P.: Maumy, M. Tetrahedron Lett., 1993, 34, 6395 -NEt2 NHEt2,0.8 GPa, CH2C12, 2d MeOH, 50°C

^^

^-/

~^sr

j..

H Matsumoto. K.: Uchida, T.; Hashimoto, S.; Yonezawa, Y.; lida, H.; Kakehi, A.; Otani, S. Heterocycles, 1993, 36, 2215 l.r-BuLi,-78°C,THF 2. ZnCl2 3. PdCl^PPhah, Dibal THF, reflux

Br 4. TsOH, EtOH Amat, M.; Hadida, S.; Bosch., J. Tetrahedron Lett., 1994, 35, 793

304

Compendium of Organic Synthetic Methods, Vol 9

Section 351

Al, KOH, MeOH, rt, 10 min NPh

PhHN

NHPh

90% (70:30 dl:meso) Baruah, B.; Prajapati, D.; Sandhu. J.S. Tetrahedron Lett., 1995, 36, 6747 NAr

XTA

NAr

TBDMS>(X

£

i

V^f

Me Ar=4-OMephenyl OH (95 : Shimizu, M.; Kami, M.; Fujisawa. T. Tetrahedron Lett., 1995, 36, 8607

5)71%

SECTION 351: AMINE - ESTER

,CHO

2. SmI2, THF, 25°C 70%

Aurrechoechea. J.M.: FernSnandez-Acebes, A. Tetrahedron Lett., 1993, 34, 549 Ph

. Im2CO , BF3-OEt2

84%

PhHN

CO2Me

THF , heat / Ph 2. NaOMe , MeOH/THF 94% —^>v Fustero. S.: Dfaz, M.D.; Carldn, R.P. Tetrahedron Lett., 1993, 34, 725 ft

AgF.EtOAc > I

MeCN.rt 15min

- CC^Et

TMS (17

:

(7:3 de) Pandey. G.: Lakshmaiah, G. Tetrahedron Lett., 1993, 34, 4861

3) 98%

Section 351

Amine - Ester

C02Et

305

,BEt 3 ,DMSO

Fe2(SO)3-H2O, hexane le Me Baciocchi. E.: Muraglia, E. Tetrahedron Lett., 1993, 34, 5015

Ph%

Me; Me.

\ ^=N

+

\

h

OSiMe33 OSiMes

_ PhHN PnHN rt.ld \

\ / \=<

>-

)

\ Montmorillonite K-10* OMe

/ '

Ph

/ (

CC^Me L

\ Me

95%

78:22 * dried under microwave conditions Texier-Boullet. P.: Latouche, R.; Hamelin, J. Tetrahedron Lett., 1993, 34, 2123

B«

H Toluene, 160°C sealed tube

Molina. P.: Pastor, A.; Vilaplana, M.J. Tetrahedron Lett., 1993, 34, 3773 1. Na+ "NHSC^Tol , 60°C THF/DMSO , 19h 2. 03 , NaOH/MeOH -78°C,3h Jumnah, R.; Williams. J.MJ. Tetrahedron Lett., 1993, 34,6619 l.SnCU.PhCN 2. OH', Na2CO3

11'^i ^

91%

Nicolini. M.: Citterio, A. Org. Prep. Proceed. Int., 1993, 25, 229 ,OSiME3 Fe-Montmorillonite 97% (96:e threo:erythro) Onaka. M : Ohno, R.; Yanigiya, N.; Izumi. Y. Synlett. 1993, 141

306

Compendium of Organic Synthetic Methods, Vol 9

P /

Section 351

,CO2Me xC<

V ^xC02Me

550oC

^/ 77%

Bureau, R.; Mortier, J.; Joucla. M. Bull. Soc. Chim. Fr., 1993, 130, 584 'Me

Bu3SnCH2CO2Et, ClCO2Me -40°C -> rt

"N

CO2Me Dhar. T.O.M.: Gluchowski, C. Tetrahedron Lett., 1994, 35, 989 Me02C,

MeO

DMSO.MS4A

O

MeO2C

^

co2Et

.

M (36

:

64) 72%

Jiang, S.; Janousek, Z.; Viehe. H.G. Tetrahedron Lett., 1994, 35, 1185

Vy

/S^ /=\ /\ M^—N \ 6 X

t r

r

400-500°C, 16 torr •*

^ I ^=7 60%

much lower yields with 8-membered rings r Jourdain, F.; Pommelet. J C. Tetrahedron Lett., 1994, 35, 1545 •*~TM. J.

LiBHEt3,SiHEt3 0*^./^

^ BF3-OEt2 ^ 85% Boc Boc Pedregal. C.: Ezquerra, J.; Escribano, A.; Carrefio, M.C.; Garcia Ruano, J.L.G. Tetrahedron Lett., 1994, 35, 2053

Section 351

Amine - Ester

307

2eq. CO,SnCl2

"

V^^-i/ H

Pdd2(PPh3)2 ^-^ 'NO2 Akazome, M.; Kondo, T.; Watanabe. Y. J. Org. Chem., 1994, 59, 3375

.BBr 3 N

2. H 2 , Pd-C, AcOH

\

^a

62%

- rx

EtO^C

N v

/ EtCH^

X^^

88x75% Jefford. C.W.: Thornton, S.R.; Sienkiewicz, K. Tetrahedron Lett., 1994, 35, 3905 BOP,MeOH,CH 2 Cl 2

l"

"

-20°°c -

xX

^

xX

^

BOP = benzotriazol- 1 -yloxy (dimethylamino)phosphonium hexafluorophosphate Kim, M.H.; Patel. D.V. Tetrahedron Lett., 1994, 35, 5603

e' , AcONa

^ 47%

Torii. S.: Okumoto, H.; Genba, A. Synlett, 1994, 217 BnNH 2 ,10% La(OTOs , CH2C12 'CO2Et NHBn 95%

Matsubara, S.; Yoshioka, M.; Utimoto. K. Chem. Lett., 1994, 827

C02Me

PhH, AIBN, heat

Undheim. K.: Williams, L. /. Chem. Soc. Chem. Commun., 1994, 883

308

Compendium of Organic Synthetic Methods, Vol 9

Section 351

(iPr)2NH,50°C.3KBar cat. Yb(OTf)3 80% (13% with no catalyst 17% with catalyst at 1 Bar) Tenner. G. Tetrahedron Lett., 1995, 36, 233 Br

1.3 eq.bu 3 SnH, 0.15 AIBN PhH (0.025 M), reflux, 6h

C02Et N^^^

syringe pump addition , 5h

j

96% (59:41 - trans: cisl) Lee. E.: Kang, T.S.; Joo, B.J.; Tae, J.S.; Li, K.S.; Chung, C.K. Tetrahedron Lett., 1995, 36, 417

I

l.DMSO,(COCl)2

A *. // \

2.NEt3

70% ^

Gentilucci, L.; Grijzen, Y.; Thijs, L.; Zwanenburg. B. Tetrahedron Lett., 1995, 36, 4665

PhCHO

\ OSiMe3 >=( , PhNH2 , rt / OMf =^

*PhHN

10% Yb(OTf)3, MS 4A, CH2C12

^^^ ^ >C /\

90% Kobavashi. 58.: Araki, M.; Yasuda, M. Tetrahedron Lett., 1995, 36, 5773 \

OSiMe3

=/

NHPh C02Me

Phh- "

5% Yb(OTf)3 , CH^C12 , 0°C

Kobavashi. S.: Araki, M.; Ishitani, H.; Nagayama, S.; Hachiya, I. Synlett, 1995, 233 CO2Me

c

,hv

N_H \

/

^ anthraquinone, MeCN

/ / \

\ N /

/—C02Me / 93%

Das. S.: Kumar, J.S.D.; Shivaramayya, K.; George, M.V. J. Chem. Soc., Perkin Trans. L, 1995, 1797

Section 352

vi ^

Amine - Ether

309

.xr—CO2Me Ph—<J 35% MeO£CH=N2 ^— ph Moran, M.; Bernardinelli, G.; Muller, P. Helv. Chim. Acta, 1995, 78, 2048 DK Pn

l%[Rh2(OAc)4],CH^Cl2

Ph

-

N2CHC02Et,CH2Cl2

^

fc

Ph

Cu(OTf)2, -25°C

^ Pti' ^r

^^/"i/"\ T~*»

"C02Et

v

riL.^

Ptf

^/"

"CO2Et

(1.7 : 1) 80% Rasmussen, K.G.; Jorgensen. K.A. J. Chem. Soc. Chem. Commun., 1995, 1401 Ph \ N

Ph \ ^ /^v H|IIIPQ gt 2 CH2C12, bis-oxazoline ligand N """ N2CHCO2Et, CuPF6(MeCN)4

™

P\ -|_ N

Ph

Ph^

(4 : 1) 37% 44% ee 35% ee Hansen, K.B.; Finney, N.S.; Jacobsen. E.N. Angew. Chem. Int. Ed. Engl., 1995, 34, 676 Related Methods:

Section 315 (Carboxylic Acid - Amide) Section 316 (Carboxylic Acid - Amine) Section 344 (Amide - Ester)

SECTION 352: AMINE - ETHER, EPOXIDE, THIOETHER

OTBDMS TBDMS

9 J r "^

l.Dibal

Ph

2

' / 3.H20

(91 : 9) 43% Cainelli. G.: Pammzio. M.: Contento, M.; Giacomini, D.; Mezzina, E.; Giovagnoli, D. Tetrahedron, 1993, 49, 3809

310

Compendium of Organic Synthetic Methods, Vol 9

Section 352

r-Bu

-f-Bu 1. PhSeBr , CH2C12,0°C

90%

2.NaBH4,MeOH

_ ^

_ —

SePh

De Kimpe, N.; Boelens, M. J. Chem. Soc. Chem. Commun., 1993, 916 hv (254 nm, Quartz), acetone 2h

(48% conversion) Cossv. J.: Guha, M. Tetrahedron Lett., 1994, 35, 1715

Of-Bu

l.NaN 3 ,ICl 2. LiAlH4 3. PhCOCl

ca. 30%

4. Nal, acetone

p

ca. 50% Eastwood, F.W.; Perlmutter, P.; Yang, Q. Tetrahedron Lett., 1994, 35, 2039

OH

PhSeCl, CH2C12 -78°C -» rt, 18h

OC- * CC CO2Et

(5 Cooper, M.A.; Ward. A.D. Tetrahedron Lett., 1994, 35, 5065

CO2Et

:

1) 61%

NHiPr 1. NBS , (BzO)2, CC14, heat C1

2. iPrNH2, ether, TiCl4 3.NaBH4,MeOH

/
De Kimpe. N.: Stanoeva, E. Synthesis, 1994, 695

Section 353

Amine - Halide

311

O

,rt,ld PIT

, CO (1 atm)

N

^^

|

OSiMe3

H Watanabe. Y.: Nishiyama, K.; Zhang, K.; Okuda, F.; Kondo, T.; Tsuji, Y. Bull. Chem. Soc. Jpn., 1994, 67, 879

^ C8Hr/

\

l.NHEt2,CH£l 2 /

2 PhOH NaOH

-

.

.

/-< u

•

CgHl7

C8H17

61% Richardson, P.P.; Nelson, L.T.J.; Sharpless. K.B. Tetrahedron, Lett., 1995, 36, 9241

cr

N

6:12) 66% trans:cis Naito. T.: Honda,Y.; Miyata, O.; Ninomiya, I. J. Chem. Soc., Perkin Trans. I., 1995, 19 (82

:

SECTION 353: AMINE - HALIDE, SULFONATE

^-

or

v\

a

0.5 MeOH \ ff 0.01Et3NHCl near quant. Gervat, S.; Leonel, E.; Barraud, J-Y.; Ratovelnmanana. V. Tetrahedron Lett., 1993, 34, 2115 "Ni2B", H20,15°C , 30 min "Ni2B" = Ni(OAc)2-4 H2O/NaBH4 Seltzman. H.H.: Berrang, B.D. Tetrahedron Lett., 1993, 34, 3083

312

Compendium of Organic Synthetic Methods, Vol 9

,h

CF3SiMe3, THF Et4NF,15h,rt ^

Section 354

F

N

I H ix, C.P.; Khatimi, N.; Laurent. AJ. Tetrahedron Lett., 1994, 35, 3303

,CO2Et

ir—*T

, HCl(g), rt O

CN

Folev. L.H. Tetrahedron Lett., 1994, 35, 5989 SECTION 354: AMINE - KETONE

JUL,

Ph

.H

. Si02

microwave (300W) 3min

^=\

-I1?

/ \^>

V=o

/ P/

89%

Rechsteiner, B.; Texier-Boullet, F.; Hamelin. J. Tetrahedron Lett., 1993, 34, 5071

, THF

O'Li* 23 C ° 'N F Kiselyov, A.S.; Strekowski. L. J. Org. Chem., 1993, 58, 4476

Pd(OAc)4, MeCN 25°C TM

X

I

hv , 9,10-dicyanoanthracene

78% Zhang, X.; Jung, Y.S.; Mariano. P.S.: Fox. M.A.: Martin, P.S.; Merkert, J. Tetrahedron Lett., 1993, 34, 5239

Section 354

Amine - Ketone

313

hv

O Winkler. J.D.: Siegel, M.G. Tetrahedron Lett., 1993, 34, 7697

>

Me

hv, 9,10-dicyanoanthracene MeOH/MeCN

Bn

Bn 23% at 73% conversion

TM

Khim, S.K.; Mariano. P.S. Tetrahedron Lett., 1994, 35, 999

-f. V\

/

/ \

PhNH2, PhH, reflux

H> O

O

Mh

90% Adembri. G.: Celli, A.M.; Lampariello, L.R.; Scotton, M.; Sega, A. Tetrahedron Lett., 1994, 35, 4023 TT

-NH2

l.PhCHO 2.TMSOTf,MeCN acetophenone

^ ^^^

N / ^ "^^

Ph

n '-

N'

\ ^ Ph N 43% Moutou, J.L.; Schmitt, M.; Wermuth, C.G.; Bourguignon, JJ. Tetrahedron Lett., 1994, 35, 6883 TMS

Eu(fod)3 H

\ H 56% Degnan, A.P.; Kim, C.S.; Stout, C.W.; Kalivretenos. A.G. J. Org. Chem., 1995, 60, 7724

314

Compendium of Organic Synthetic Methods, Vol 9

Section 354

hv, DCA, MeCN DCA. = 9,10-dicyanoanthracene

SiMe3

syn, 81% less selective with pyrrolidine derivatives anti, 18% Hoegy, S.E.; Mariano. P.S. Tetrahedron Lett., 1994, 35, 8319

Cu(acac)2, PhH , reflux

*• ^v />—\v

—

76%

Clark. J.S.: Hodgson, P.B. J. Chem. Soc. Chem. Commun., 1994, 2701

HO-I 20% Bu4NReO4, DCE, reflux, 2h

MeO Kusama, H.; Uchiyama, K.; Yamashita, Y.; Narasaka. K. Chem. Lett., 1995, 715

,OMe PhCHO

Me

, ArNH 2 , THF-H2O

NHAr

10% Yb(OTf)3 AT = 4-chlorophenyl Kobavashi. S.: Ishitani, H. /. Chem. Soc. Chem. Commun., 1995, 1379

90%

Section 356

Amine - Alkene

315

CC^Me

CC^Me

Ph >

10% NiBr2(PPh3)2

Me Me Shida, N.; Kubota, Y.; Fukui, H.; Asao, N.; Kadoata, I.; Yamamoto. Y. Tetrahedron Lett., 1995, 36, 5023

SECTION 355: AMINE - NITRILE

3% BF3»OEt2 , 0°C , 4h NHTs

(2-6

',N—Ts

Bergmeier. S.C .: Seth, P.P. Tetrahedron Lett., 1995, 36, 3793 SECTION 356: AMINE - ALKENE l.(CH20)n,90°C

Bn

90°C , 30 min Petasis. N.A.: Akritopoulou, I. Tetrahedron Lett., 1993, 34, 583 1. sec-BuU, -78°C 2. Mel

N^

4. SmI 2 , THF-HMPA

Ibafiez, P.L.; Naiera. C. Tetrahedron Lett., 1993, 34, 2003

N » - NHTs :

1) 84%

316

Compendium of Organic Synthetic Methods, Vol 9

Section 356

r-Bu r-Bu

(72 I : Wegman, S.; Wurthwein. E.U. Tetrahedron Lett., 1993, 34, 307

>-

Me

13)2

^/

28)

41%

+

1

Ph in Toluene 10% 85% in DMF 72% 2% Filippini. L.: Gusmeroli, M,; Riva, R. Tetrahedron Lett., 1993, 34, 1643

, Bu

1. LDA , -78°C THF^xylene 2. xylene , reflux , 4h

° I . 0 ^r^ ^NHBu

+

(99.5

:

0.5) 92%

Tsunoda. T.i Tatsuki, S.; Shiraishi, Y.; Akasaka, M.; Ito, S. Tetrahedron Lett., 1993, 34, 3297

OMe

1. BF3OEt2,THF 3. allyl bromide, 4.10% aq. Na2CO3

rt

I II

Giammaruco, M.; Taddei. M.: Ulivi, P. Tetrahedron Lett., 1993, 34, 3635

65%

Section 356

Amine - Alkene

317

2 EtO 2 <X x CO 2 Et • f Palacios. F.: Perez de Heredia, I.; Rubiales, G. Tetrahedron Lett., 1993, 34, 4377

H

SnCU, 20°C M excess Me2C=CH2M (30

x

' :

70) 61%

Mikami. K.: Kaneko, M.; Yajima, T. Tetrahedron Lett., 1993, 34, 4841 , AIBN , 0.05M (syringe pump), 2h

NHPh

-SePh

23% Schwan. A.L.: Refvik, M.D. Tetrahedron Lett., 1993, 34, 4901

45%

Me3SK (CH20)n, p-tsOH-H20 MeCN)60°C

Bn H Castro, P.; Overman. L.E.: Zhang, X.; Mariano. P.S. Tetrahedron Lett., 1993, 34, 5243

£HO

r-BuNH2, MS 3A, 2h CH2C12,22°C M&n,,, 94%

Sigman, M.S.: Eaton. B.E. Tetrahedron Lett., 1993, 34, 5367

318

Compendium of Organic Synthetic Methods, Vol 9

Section 356

1. LDA, THF 2. ZnClrOEt2

Barluenga. J.: del Pozo Losada, C.; Olano, B. Tetrahedron Lett., 1993, 34, 5497 Bi/Bu4NBr, MeCN r»i^

\^

'Br Bhuyan, P.J.; Prajapati, D.; Sandhu. J.S. Tetrahedron Lett., 1993, 34, 7975

^^

95%

u ene bv

• "" \ CH2OEt

2. 23°C, 12h 3. TBAF

^ CH2OEt Knapp. S.: Albaneze, J.; Schugar. H.J. / Org. Chem., 1993, 58, 997 f/

\

NHMe\ BF3OEt2,Tol

MeO (66 Beholz, L.G.; Stille. J.R. J. Org. Chem., 1993, 58, 5095

PhI,Pd(PPh 3 )4,K 2 CO3 DMF, 70°C NHBn Davies, I.W.; Scopes, D.I.C.; Gallagher, T. Synlett, 1993, 85

•x.

^^~~~»^ ss

N I Bn

Ph

71%

Section 356

Amine - Alkene

319

SnBu3 11 N™ \

,J/

B

\\j__M, Me

BuLi.THF -78°C -> rt

(17 : Coldham. I. ]. Chem. Soc., Perkin Trans. L, 1993, 1275

83) 65%

.NTsOH . heat. 2h _

80% Leurs, S.; Vanderbulcke-Coyette, B.; Viehe, H.G. Bull. Soc. Chim. Belg., 1993, 102, 645 NHPh

Jin, S.-J.; Araki, S.: Butsugan. Y. Bull. Chem. Soc. Jpn., 1993, 66, 1528 x Bn

SEt

N A1C13 , CH2C12, rt

77% Tohyama, Y.; Tanino, K.; Kuwaiima. I. J. Org. Chem., 1994, 59, 518

Br 'NHTs

, 5%Pd(OAc)2

10% P(o-Tol)3 , Na2C(>3 I 2 BU4NC1,90°C, Id " TS Larock. R.C.: Yang, H.; Weinreb. S.M.: Hetr, R.J. J. Org. Chem., 1994, 59, 4172

320

Compendium of Organic Synthetic Methods, Vol 9

>c,

Section 356

2 eq. BuaSnH, AIBN, PhH » reflux

89% NHNM62 Bemard-Henriet, C.; Grimaldi, J.R.; Hatem. J.M. Tetrahedron Lett., 1994, 35, 3699

Ph

Me 1) 65%

Pearson. W.H.: Jacobs, V.A. Tetrahedron Lett., 1994, 35, 7001 PhNHOH, FeCl2/FeCl3 72%

NHPh Srivastava, R.S.; Nicholas. K.M. Tetrahedron Lett., 1994, 35, 8739 H

LDA

Ahman, J.; Somfai. P. 7. Am. Chem. Soc., 1994, 116, 9781

l.Ni(cod)2,MeCN Br

2. 16 NaBH4 , 6 MeOH Sold, D.; Cancho, Y.; Llebaria, A.; Moret5, J.M.; Delgado. A. / Am. Chem. Soc., 1994, 116, 12133

Section 356

Amine - Alkene

321

1% (PCy3)2Cl2Ru=CHCH=CPh2

Ts—N

PhH, eflux, 6h

\

OA •OAc Kinoshita, A.; Mori. M. Synlett. 1994, 1020

OAc

2 eg. morpholine , neat MS4A, 30 min

92%

Fisher. G.B.: Lee, L.; Klettke, F.W. Synth. Commun., 1994, 24, 1541 Ph

-^ \ N

Zn(Cu), MeOH, H 2 O, rt ultrasound

_

_

53% De Kimpe. N.: Jolie, R.; De Smaele, D. J. Chem. Soc. Chem. Commun., 1994, 1221

CCty-Bu N

LDA, THF, -78°C N H

63% Coldham. L: Collis, A.J.; Mould, R.J.; Rathmell, R.E. Tetrahedron Lett., 1995, 36, 3557

Et2N HNEt2, 20% Et3NHI, THF 10% Pd(dba)2,2 PPh3 65°C, 18h

70% (96:4 E:Z) Besson, L.; Gor6, J.; Cazes. B. Tetrahedron Lett., 1995, 36, 3857

C?Hl5

8%

322

Compendium of Organic Synthetic Methods, Vol 9

NaCH(CO2Me)2,5% Pd(PPh3)4 LiCl, DMSO, 60°C

Section 356

I

CC^Me

53%

\x^ Vicart, N.i Gazes, B.; Gore. J. Tetrahedron Lett., 1995, 36, 5015 J C H

3 ?

fin

h

ether , -50°C -» -10°C , 4h

>=/ '

\/ Ph

Ph

PiOi-"" kOiPr

82%

Gao, Y.; Harada, K.; Usato, F. Tetrahedron Lett., 1995, 36, 5913 Ph

Bu3Snx

56% ru

15% Yb(OTf)3 , CH£12 , rt

ru

Bellucci, C.; Cozzi. P.G.: Umani-Ronchi. A. Tetrahedron Lett., 1995, 36, 7289 .™ , ,, Me3cSiQ 2. aq. NH4F

NHPh Ph-^^X^X^^.

Wang, D.-K.; Dai. L.-X.: Hou. X.-L. Tetrahedron Lett., 1995, 36, 8649

Ph 5 PhMgBr, 5% NiCl^PPhs^

THF, 22°C C6H13

(8 : 1) 80% (5:1 cis:tranws) Didiuk, M.T.; Morken, J.P.: Hovevda. A.H. 7. Am. Chem. Soc., 1995, 117, 7273

Section 357

Ester - Ester

323

BF3-OEt2,210°C,2h

_

47%

Anderson. W.K.: Lai, G. Synthesis, 1995, 1287

Br 5 eq. 1-octene, DMA 5 eq. morpholine, 100°C 10 eq. H20, 2d

(85 Larock. R C..: Tu, C. Tetrahedron, 1995, 51, 6635

:

SECTION 357: ESTER - ESTER C02Et , AIBN, Tol reflux, 2h

72% °*\

/**-<] Ph

Kim. S.: Kee, I.S. Tetrahedron Lett., 1993, 34, 4213

Ti(OiPr)Cl3,

C02Me

3. p-TsOH, toluene *

ph

"v^

(92 Shimada, S.; Tohno, I.; Hashimoto, Y.; Saigo. K. Chem. Lett., 1993, 1117

324

Compendium of Organic Synthetic Methods, Vol 9

Ph

OH

r

1/50 CoCl2,42h

Section 357

_

DME , O2 , 80°C PIT Li, P.; Alper. H. Can. J. Chem., 1993, 71, 84

(1

:

Ph^

5) quant.

acetone , Sml2 , THF 4% Fe(dbm)3 , reflux CO2Me

I

74%

Imamoto. T.: Hatajima, T.; Yoshizawa, T. Tetrahedron Lett., 1994, 35, 7805 MeQ

OTMS \ OMe

Pd(PPh3)4,TlOAc,HF reflux, Id

^

N

ff

COaMc

Sakamoto. T.: Kondo, Y.; Masumoto, K.; Yamanaka, H. J. Chem. Soc., Perkin Trans. 1., 1994, 235 PhCHO, Cp2Sn(thf)2

{?

Ph

Tol, 0°C -> 25°C

S^^Q"

^^

^CT

O " Ph

77% Takano, M.; Kikuchi, S.; Morita, K.; Nishiyama, Y.; Ishii. Y. J. Org. Chem., 1995, 60, 4974

, Ac2O, PhH

_

M

OAc

0

, « JJ P v^ , I4h 1"" \J

1 11

V^

67%

Bhat, S.; Ramesha, A.R.; Chandrasekaran. S. Synlett, 1995, 329 Also via Dicarboxylic Acids: Hydroxy-esters Diols

Section 312 (Carboxylic Acids - Carboxylic Acids) Section 327 (Alcohol - Ester) Section 323 (Alcohol - Alcohol)

Section 358

Ester - Ether

325

SECTION 358: ESTER - ETHER, EPOXIDE, THIOETHER Bu3SnH , AIBN , PhH reflux , 6h , syringe pump 02Et Br Lee. E.: Tae, J.S.; Lee, C.; Park, C.M. Tetrahedron Lett., 1993, 34, 4831

SiMe3

02C N.

i. CsF , MeCN Me02C

\

C02Me

/

^V

f

95%

jC02Me

S

92%

^/C / IT >«^ PIT XX

Hojo, M.; Ohkuma, M.; Ishibashi, N.; Hosomi. A. Tetrahedron Lett., 1993, 34, 5943 O

(TfO)2Sn(bis-amine) OTMS

CH 2 Cl 2 ,9h,-78°C PhCHO

OTMS

II "~

^^^Ph

86% (93:7 syn:anti) Kobayashi, S.; Uchiro, H.; Shiina, I.; Mukaiyama, T. Tetrahedron, 1993, 49, 1761 1.3Bu3SnH 0.25 AIBN CHO

0.03M PhH reflux, 8h

(46 : 54) 91% Lee. E.: Tae, J.S.; Chong, Y.H.; Park, Y.C.; Yun, M.; Kim, S. Tetrahedron Lett., 1994, 35, 129 OTMS

40%SnO

.CHO

SEt

20%Sn(OTf)2 ^ ^ chiral diamine slow addition (3h) Kobavashi. S.: Kawasuji, T.; Mori, N. Chem. Lett., 1994, 111

^

-^ -SEt „„ .,_„ 61% (62% ee)

326

Compendium of Organic Synthetic Methods, Vol 9

Section 359

Rh2(OAc)4 , MeOH

H(

49% Cox, G.G.; Haigh, D.; Hindley, R.M.; Miller, D.J.; Moody. C.J. Tetrahedron Lett., 1994, 35, 3139 O

I. PhCHO, ZnCl2 , CH2C12 2. CAN, MeOH, -78°C , CO

\ 40%

ph

^-^

Jiang, S.; Turos. E. Tetrahedron Lett., 1994, 35, 7889 PtCl2-AgPF6, CH2C12 MeO^

^

CO2Me

7CO2Me

»MeOH

MeO^

CO2Me

quant. Kataoka, Y.; Matsumoto, O.; Ohashi, M.; Yamagata, T.; Tani. K. Chem. Lett., 1994, 1283

SECTION 359: ESTER - HALIDE, SULFONATE F [CF2Br2/Zn, DMF, 2h, rt] HMPA, CuBr, 60°C , 40 min

Mawson, S.D.; Weavers. R.T. Tetrahedron Lett., 1993, 34, 3139 )H

»

^^

^^^^

^^^^

— n

^ OH

3 HBr, AcOH, 16h

62%

B

OH \

2.2 MeCOBr, dioxane, 16h

El Anzi, A.; Benazza, M.; Fr6chou, C.; Demaillv. G. Tetrahedron Lett., 1993, 34, 3741

Section 359

Ester - Halide

327

CH2C12,18h to-(sym-collidine) iodine(I) hexaflurophosphate Simonot, B.; Rousseau. G. J. Org. Chem., 1993, 58, 4 C02Me . Ti(OTf)4 , CH2C12 C02Me 2.12,01*32 89% Kitagawa, O.; Inoue, T.; Hirano, K.: Takuchi. T. 7 Org. Chem., 1993, 58, 3106

KI, sodium persulfate, NaHCC>3 H2O

J.A.VX

Royer, A.C.; Mebane, R.C.; Swafford, A.M. Synlett, 1993, 899 BzCl, 0.4 SmI3 , MeCN , it BzO

Yu, Y.; Zhang. Y.: Ling, R. Synth. Commun., 1993, 23, 1973 1. HC=CCO2H , NCI, CH2C12 2. (BzO)2 , PhH , eflux 78x44%

O

•o Haaima, G.; Lunch, M.-J.; Routledge, A.; Weavers. R.T. Tetrahedron, 1993, 49, 4229 , DMSO BEt3, it (open to air) 14 eq.

\

ll

*-

\

Bachiocchi. E.: Muraglia, E. Tetrahedron Lett., 1994, 35, 2763

/

wz

" 54%

328

Compendium of Organic Synthetic Methods, Vol 9

Bll2

\

C 2H

X

°

1-mcpba

/

Section 359

/Av^

2.I 2 ,NaHCO 3

\ y

/ '''<*«, i

50%

Reetz. M.T.: Lauterbach, E.H. Heterocycles, 1993, 35, 627

1jfe

1

1 1

^ //

\^Y ^-CF>

CF2I , aq. MeCN

80%

J

>!

(95:5

E:Z)

Lu. X.: Wang, Z.; Ji, J. Tetrahedron Lett., 1994, 35, 613 Ac

I

AcCl, 5% ZnCl2 re, In

Cl (3 : 97) 95% Mimero, P.; Saluzzo, C.; Amouroux. R. Tetrahedron Lett., 1994, 35, 1553

Cl DMF 2. LiOMe, MeOH 96% Bellesia, F.; Boni, M.; Ghelfi. F.: Pagnoni, U.M. Tetrahedron Lett., 1994, 35, 2961

F2Br

<

r

B U3 SnH,AIBN,PhH reflux, 1-15 h addition

Buttle, L.A.; Motherwell. W.B. Tetrahedron Lett., 1994, 35, 3995

F

F

Section 359

Ester - Halide

329

BuO s

TBAB , 90°C , 6h

Kameyama, A.; Kiyota, M.; Nishikubo. T. Tetrahedron Lett., 1994, 35, 4571 AcCl,CP2YCl

Cl

CH2C12,13h

™^\^\ ph

(88 Oian. C.: Zhu, D. Synth. Commun., 1994, 24, 2203

Ac +

I J,h :

C1

12) 95%

I 2 , Pb(OAc)2'3 H2O , AcOH

rt,6h

^*r 85%

Bedekar, A.V.; Nair, K.B.: Soman. R. Svnth. Commun., 1994, 24, 2299

PhMe3N+ Br3-

78% Collado. I.G.: Galin, R.H.; Massanet, G.M.; Alonso, M.S. Tetrahedron, 1994, 50, 6433

0.3 Cu(bpy)Cl, DCE reflux, 18h 57% (70:30) Pirrung, F.O.H.; Hiemstra. H.: Speckamp. W.N.: Kaptein, B.; Schoemaker, H.E. Tetrahedron, 1994, 50, 12415

330

Compendium of Organic Synthetic Methods, Vol 9

JL

25°C, 18h

1 11

Section 360

V

70%

Bhar, S.; Ranu. B.C. J. Org. Chem., 1995, 60, 745 SECTION 360: ESTER - KETONE

l.Br Br Py, e t h e r * * ^^ 53% 2. TMSC1, ether ^ Zn, reflux Landi Jr., J.J.; Garafalo, L.M.; Ramig. K. Tetrahedron Lett., 1993, 34, 211

„ T , CnH23

,C02Me

2% Rh2[O2CCH(Bn)NPhth]4 CC^Me

*~

|

)

CH2C12,0°C

CO2Me

Ph (46%ee, R) Hashimoto, S.; Watanabe, N.; Sato, T.; Shiro, M.; Ikegami. S. Tetrahedron Lett., 1993, 34, 5109 WNHPh -^*'*^\. CO^Et

1.7 PhI(OH)OTs, CDC13 rt

'

9h

ft —'—^v^ CO^Et

noof "o%

Barton. D.H.R.: Jaszberenvi. J.Cs.: Shinada, T. Tetrahedron Lett., 1993, 34, 7191 PhCHO, EtNO2 A1C13,100°C, 5h

Ph

Sartori. G.: Bigi, E.; Maggi, R.; Bemardi, G.L. Tetrahedron Lett., 1993, 34, 7339

Section 360

Ester-Ketone

331

PhsFV.

CO2Et

48h, 30°C CC^Et

2. aq. HC1, CHC13

Ph 92x99% Hatanaka. M.: Himeda, Y.; Imashiro,; Tanaka, Y.; Ueda, I. 7. Org. Chem., 1994, 59, 111

1. (COC1)2, hv 2. MeOH

Bashir-Hashemi. A.: Hardee, J.R.; Gelber, N.; Qi, L.; Axenrod, T. J. Org. Chem., 1994, 59, 2131

,CO2Me '

KH,THF,18-c-6,rt

Habi, A.; Gravel. D. Tetrahedron Lett., 1994, 35, 4315

'Ac

j? ph-^Cl

OAc , 4% Pd(PPh3)2Cl2

8% CuCN, 75°C, 18h

74% Ye, J.; Bhatt, R.K.; Falck. J.R. / Am. Chem. Soc., 1994, 116, I

O CO2r-Bu

0

0

Lvgo. B. Tetrahedron Lett., 1994, 35, 5073

96%

332

Compendium of Organic Synthetic Methods, Vol 9

Section 360

O

MeO2C Chuang. C.-P.: Wang, S.-F. Tetrahedron Lett., 1994, 35, 4365 1. NaH , DME, 40°C 2. BuLi

or

^~^

3. PCC, A12O3, CH2C12

y-^. X

A

o=(

\<^k

[

)

J/

^—

93x68x68% Piers. E.: Cook, K.L.; Rogers, C. Tetrahedron Lett., 1994, 35, 8573

KMnO4 , CuSO4«5 H2O OH

47%

4h

Das, J.; Chandrasekaran. S. Tetrahedron, 1994, 50, 11709 H

e-,CH 2 Cl 2 -H 2 0 NaBBr2

I? Plr

^^

Maekawa, H.; Ishino, Y.; Nishiguchi. I. Chem. Lett., 1994, 1017 )H

aq. f-BuOOH , 1% CuCl2 , 3% TBAB ,25°C, Id 96%

Feldberg, L.; Sasson. Y. J. Chem. Soc. Chem. Commun., 1994, 1807

Section 360

Ester - Ketone

333

ys

(Me3Si)3SiH, AIBN

'

PhH, 80°C , 0.01M

0

^/~^

"O

Rvu. I.: Nagahara, K.; Yamazaki, H.; Tsunoi, S.; Sonoda. N. Svnlett. 1994, 643

BuaSnH, AIBN PhH, 80°C

(9 Enholm. E.J.: Kinter, K.S. J. Org. Chem., 1995, 60, 4850

^^

e -, DMF/LiClO4

T

:

f

1) 75%

JL

OL

H

^^ V

67% Barba, F.: Quintanilla. M.G.: Montero. G. J. Org. Chem., 1995, 60, 5658

o

,OH

KMnO4, pH 7 *OEt Tatlock. J.H. J. Org. Chem., 1995, 60, 6221 O

1. CuBr2, PW(OH)OTs, 0°C 2. DMAP, dimethyldioxirane CH2C12,0°C O 1st step is quant

Coats, S.J.; Wasserman. H.H. Tetrahedron Lett., 1995, 36, 7735

334

Compendium of Organic Synthetic Methods, Vol 9

a V'y

-OPh

Section 361

> THF

PhCHO

*• II 2. p-TS A, AcOH, 90°C , Id Ph—^ 'OAc Katritzkv. A R.: Yang, Z.; Moutou, J.-L. Tetrahedron Lett., 1995, 36, 841

Br SmI2, THF , -35°C, 5 min

o

o

~/

'

\

88x78%

"

u

O 72%

Park, H.S.; Lee, I.S.; Kim. Y.H. Tetrahedron Lett., 1995, 36, 1673 REVIEW: "Alternate Preparations Of a-Keto Esters From Acid Chlorides," Katritzky. A.R.: Wang, Z.; Wells, A.P. Org. Prep. Proceed. Int., 1995, 27, 457 Also via Ketoacids Hydroxyketones

Section 320 (Carboxylic Acid - Ketone) Section 330 (Alcohol - Ketone)

SECTION 361: ESTER - NITRILE

,CHO Ph rn

NC Pd^dba)3«CHCl3, dppe MeCN, Id

Nemoto, H.; Kubota, Y.; Yamamoto. Y. 7. Chem. Soc. Chem. Commun., 1994, 1665

OH TB AF , THF, Ih LiCl, it

Stojanova, D.S.; Milenkov, B.; Hesse. M. Helv. Chim. Acta, 1993, 76, 2303

Section 362

Ester - Alkene

SECTION 362:

335

ESTER - ALKENE

This section contains syntheses of enol esters and esters of unsaturated acids as well as ester molecules bearing a remote alkenyl unit.

O CO2H

!.Br2,NaHCO3 2.AgN03,AcOH

I \ l^ ^

Bu

Bu

66 x 50%

Black. T.H.: Huang, J. Tetrahedron Lett., 1993, 34, 1411 l.K 2 CO 3 ,5kbar ,10%P(2-furyl)3 ^ =

'

^

61%

3. HC=CCMe2OAc, DMSO 20°C, 14h

__ "'

'

Bouyssi, D.; Gore, J.; Balme, G.; Louis, D.; Wallach, J. Tetrahedron Lett., 1993, 34, 3129

•Me MpO

Me<X

^<^

^

^Me

CO

//

'

Pd(OAc)2(dppp) *OTf Ciattini, P.O.; Mastropietro, G.; Morera, E.; Ortar. G. Tetrahedron Lett., 1993, 34, 3763

Br

CO H

Ph-C=CH , NEt3, MeCN , rt PdCl2(PPh3)2, Cul, lOh

Ph

(>97:3

Z:E)

Lu. X.: Huang, X.; Ma, S. Tetrahedron Lett., 1993, 34, 5963

Me3SiCH=C=O, PhH

51%

MC3sio/

•OSiMe3

reflux, 3d

//

Me3Si Ito, T.; Aovama. T.: Shioiri. T. Tetrahedron Lett., 1993, 34, 6583

^rf

cr

^n

o

336

Compendium of Organic Synthetic Methods, Vol 9

Section 362

'JBn

^^.C02Me

MeNO2,80°C

Q

^X/.

OBn

Markd. I.E.: Evans, G.R. Tetrahedron Lett., 1993, 34, 7309 V

;O

(30

:

70) 29%

[60:40 E:Z\ Bhatia, B.; Reddy, M.M.; Iqhal. J. Tetrahedron Lett., 1993, 34, 6301

O2Et

1. SnCl2

"^r

i i

81% 2

-

- -CHO ,ether,rt

Fouquet E.: Gabriel, A.; Maillard, B.; Pereyre, M. Tetrahedron Lett., 1993, 34, 7749

—- co° 5%Pd(OAc)2,2NaOAc

DMSO , o2

/T'x

Larock. R.C.: Hightower, T.R. J. Org. Chem., 1993, 58, 5298 ~"

1. PhSeCH2CH2OH, EDC

DMAP.DMF 2.H202,THF 3. iPr^IH , CHC13 , reflux Weinhouse, M.I.; Janda. K.D. Synthesis. 1993, 81

Bn

92x90%

Section 362

Ester - Alkene

337

70% Annbv. U.: Stenkula, M.; Andersson. C.-M. Tetrahedron Lett., 1993, 34, 8545

30%

, PhH, rt, 8h

•CO2Et HO' Guo, C.; Lu. X. J. Chem. Soc. Chem. Commun., 1993, 394 r?w~»-/-> rr. M CO2Me

-

— -

^OMe

, 0.5 BusSnH X°Me , 0.05 AIBN, reflux, 4h PhH (0.01 M), syringe pump (2h) Lee. E.: Hur, C.U.; Rhee, Y.H.; Park, Y.C.; Kim, S.Y. J. Chem. Soc. Chem. Commun., 1993, 1466 P(OEt)3 , NEt3-H2O , 120°C 8h (sealed tube) Hirao. T.: Hirano, K.: Ohshiro. Y. Bull. Chem. Soc. Jpn., 1993, 66, 2781

TTN , MeOH, 3M HC1 3-26h TIN = TKNO2)3 Y

Me

"O

° MeO Thakkar, K.; Cushman. M. Tetrahedron Lett., 1994, 35, 6441

338

Compendium of Organic Synthetic Methods, Vol 9

Section 362

Pd(OAc)2 , dppp , PhMe , MeOH reflux

Mandai. T.: Tsujiguchi, Y.; Tsuji, J.; Saito, S. Tetrahedron Lett., 1994, 35, 5701 Bl

\

[Pd(MeCN)2(PPh3)2] [BF4]2

Bu

CO , THF, 50°C HO' \

°

'

C02H (17 : 83) 92% Matsushita, K.; Komori, T.; Oi, S.; Inoue. Y. Tetrahedron Lett., 1994, 35, 5889

JL

1. NaH , TMEDA, THF, reflux 2. inverse addition to PhOCOCl

43%

Harwood, L.M.; Houminer, Y.; Manage, A.; Seeman. J.I. Tetrahedron Lett., 1994, 35, 8027 ^xx5j^xCO2Me PhCHO

pn

.

OH

^=^ 34% DABCO, microwave, 10 min CO2Me Kundu, M.K.; Mukherjee, S.B.; Balu, N.; Padmakumar, R.: Bhat. S.V. Svnlett. 1994, 444

PhCHO

-

BrCH2CO^fe, Bu 3 As, 10% Cd ^ 100°C, 20h

Zheng, J.; Shen. Y. Synth. Commun., 1994, 24, 2069

Ph

^^^ 87% (Eonly)

Section 362

Ester - Alkene

339

CO2Me TBSP = p-(f-butyl)phenylsulfonylprolinate *~ 76% (63% ee) Davies. H ML.: Peng, Z.-Q.; Houser, J.H. Tetrahedron Lett., 1994, 35, 8939 O

.5% Pd(OAc)2 8%PPh 3 ,1.2Ag 2 CO3,MeCN 90°C, 45 min Meyer, F.E.; Ang, K.H.; Stenig, A.G.; de Meijere, A. Synlett, 1994, 191 , CO, THF, autoclave Ph'

N

Ph PI

0

OH

RuCl2(PPh3)3-K2CO3,200 C,15h

„/ Ph

'O'

77% Kondo, T.; Kodoi, K.; Mitsudo, T.-u.; Watanabe. Y. J. Chem. Soc. Chem. Commun., 1994, 755

l.RiekeMg*,THF,rt 2. ethylene oxide , THF, -78°C 3. CO2,0°C -> rt 4.H 3 O + ,110C 69%

Rieke. R.D.: Sell, M.S.; Xiong, H. J. Org. Chem., 1995, 60, 5143 nBu

3

Cu(NO3)2, THF.rt

SPh ]

CO2Me [ 65%

SPh

CO2Me SPh Beddoes, R.L.; Cheeseright, T.; Wang, J.; Ouavle. P. Tetrahedron Lett., 1995, 36, 283

340

Compendium of Organic Synthetic Methods, Vol 9

Section 362

CO2Me

SePh

»•

CQzM / pnHG=*

_ nuTJJ^_

CHCl 3 ,4h

96%

\

SePh Huang, Z.-Z.; Huang. X.: Huang. Y.-Z. Tetrahedron Lett., 1995, 36, 425

5% Cl2Pd(PPh3)2 . 4 NEt3 20 aim CO, PhH , 110°C, lOh

o

PK

"or

-o

99% Coperet, C.; Sugihara, T.; Wu, G.; Shimoyama, I.; Negishi. E. J. Am. Chem. Soc., 1995, 117, 3422 l.NEt 3 ,CH 2 Cl 2 ,-20 0 C

^O

2. BnOH

75% Cardillo. G.: De Simone, A.; Mingardi, A.; Tomasini, C. Synlett, 1995, 1131

CuCl2 , LiCl , MeCN PdCl2(PhCN)2

O

O

CsHu

(>97 Zhu, G.; Lu. X. Tetrahedron Asymmetry, 1995, 6, 345

JL

PhO'

'Cl

jtoluene

A1C13 ,20°C, 2h

PhO

Mavr. H.: Gabriel, A.O.; Schumacher, R. LiebigsAnn. Chem., 1995, 1583

Section 363

Ether - Ether

341

C02Me OSiMe3

MeO2C

=S=

CO2Me

BuHC====

X N OPr

ZrCU, CCLj, 0°C -» rt

>=CHBu

Mitani. M.: Sudoh, T.; Koyama, K. Bull. Chem. Soc. Jpn., 1995, 68, 1683 Related Methods:

Section 60A (Protection of Aldehydes). Section 180A (Protection of Ketones). Section 306 (Alkyne - Ester). Section 322 (Carboxylic Acid - Alkene). Section 327 (Alcohol - Ester).

Also via Acetylenic Esters: Alkenyl Acids: {3-Hydroxy-esters:

SECTION 363:

ETHER, EPOXIDE, THIOETHER - ETHER, EPOXIDE, THIOETHER

See Section 60A (Protection of Aldehydes) and Section 180A (Protection of Ketones) for reactions involving formation of Acetals and Ketals. l.DDQ,MeOH,CH 2 Cl 2 rt,ld 2. aq. NaHCO3 OMe Xu. Y.-C.: Lebeau, E.; Gillard, J.W.; Attardo, G. Tetrahedron Lett., 1993, 34, 3841

iPrOH, 20% CuCl2 5% Pd(NO)2Cl(MeCN)2 2h

50% isolated Meulemans, T.M.; Kiers, N.H.; Feringa. B.L.: van Leeuwen, P.W.N.M. Tetrahedron Lett., 1994, 35, 455 OMe

DEAD,PPh3,CH2Cl 2 ,0°C HO OH

80% (a-only) Sobti, A.; Sulikowski. G.A. Tetrahedron Lett., 1994, 35, 3661

78%

342

Compendium of Organic Synthetic Methods, Vol 9

Section 364

OMe

BTIB , EtOH SPh

OMe

BT1B =

/

7 UMe

/

/ OMe eO

(a:p = l:15) 81%

foXtrifluoroacetoxy)iodobenzene

Sun, L.; Li, P.; Zhao. K. Tetrahedron Lett., 1994, 35, 7147

,OMe

TMS-SPh, DMF SPh 87%

Miura, T.; Masaki. Y. Tetrahedron Lett., 1994, 35, 7961

OMe

p-Tol

ZnI2, THF jr

\

OSiMe2r-Bu 70% (>99% e) Kita. Y.: Shibata, N.; Fukui, S.; Fujita, S. Tetrahedron Lett., 1994, 35, 9733

SECTION 364:

ETHER, EPOXIDE, THIOETHER - HALIDE, SULFONATE L. C1CH2I, MeLi, -78°C

Me-/,

2. -78°C -> +20°C Br Barluenga. J.: Llavona, L.; Bernad, P.L.; Concell6n, J.M. Tetrahedron Lett., 1993, 34, 3173 'H

XeF2,CH2Cl2,35°C

\ Stavber, S.; Zupan, M. Tetrahedron Lett., 1993, 34, 4355

Section 364

Ether-Halide

343

Mn02,AcCl

S PIT Cl 82% Bellesia, F.; Ghelfi, F.; Pagnoni, U.M.; Pinetti. A. Gazz. Chim. Ital, 1993, 123, 289

°Me

Br 2 ,Me3SiCl,NaBr,30min

°Me

\

OMe

OMe

98% Bellesia, F.; Boni, M.; Ghelfi. F.: Pagnoni, U.M. Gazz. Chim. Ital., 1993, 123, 629

NBS , CH2C12, rt, 5 min

Br^^ .s^*^ ^Bt ^^ ^^

60% Antonioletti, R.; Magnanti, S.; Screttri, A. Tetrahedron Lett., 1994, 35, 2619

MeO£.

l.LDA.HMPA 2. acetone 3.12, NaHCO3 MeCN

....

-™™.

..«

'CO2Me

32x47% Galatsis. P.: Parks, D.J. Tetrahedron Lett., 1994, 35, 6611 OH

'

I 2 , NaHCO3 , dry MeCN 16h

\

75% *I Barks, J.M.; Knieht. D.W.: Weingarten, G.G. J. Chem. 5oc. Chem. Commun., 1994, 719

PhI(O2CCF3)2,12, CC14 83% S

D'Auria, M.; Mauriello, G. Tetrahedron Lett., 1995, 36, 4883

344

Compendium of Organic Synthetic Methods, Vol 9

Section 365

(CH20),/CH2C12, rt A1C13, Id

(4 : Metzger. J.O.: Biennann, U. Bull. Soc. Chim. Belg., 1994, 103, 393

(collidine)2r PF6' -

••

OH

CH2Cl2

N^^'

95%

Brunei, Y.; Rousseau, G. Synlett, 1995, 323

°Me

I 2 ,CAN,MeOH rt, 2h

°Me

_

(2.6 : 1) 88% Horiuchi. C.A.: Hosokawa, H.; Kanamori, M.; Muramatsu, Y.; Ochiai, K.; Takahashi, E. Chem. Lett., 1995, 13

SECTION 365: ETHER, EPOXIDE, THIOETHER - KETONE MeOL ^^ ^

>SiMe3

U

Q

QMe

OH

BF3«OEt2, MeNO2, -25°C 30min

(7:3 syn:anti) Duhamel. P.: Guillemont, J.; Poirier, J.-M. Tetrahedron Lett., 1993, 34, 4197 2% Cu(hfacac)2, CH2C12

hfacac = hexafluoroacetyl acetonate Clark. J.S.: Krowiak, S.A.; Street, LJ. Tetrahedron Lett., 1993, 34, 4385

Section 365

Ether - Ketone

345

93%

(9:1 2Me:3Me)

-OAc Ciufolini. M.A.: Rivera-Fortin, M.A.; Byrne, N.E. Tetrahedron Lett., 1993, 34, 3505 Ph2f-Bu

CH2C12, -45°C

Ph2r-BuO-4

'

Me

(96:4) where 4 = other isomers Horiguchi, Y.; Suehiro, I.; Sasaki, A.; Kuwaiima. I. Tetrahedron Lett., 1993, 34, 6077

x

MeQ

DMe

5% TMSN(S02F>2 CH2C12 , -78°C

JLr I

\

k^

Trehan, A.; Vij, A.; Walia, M.; Kaur, G.; Verma. R.D.: Trehan. S. Tetrahedron Lett., 1993, 34, 7335

p-TsOH, H 2 O, CH2C12 20°C, 12h Cossv. J.: Furet, N. Tetrahedron Lett., 1993, 34, 7755

346

Compendium of Organic Synthetic Methods, Vol 9

Section 365

[RhCl(C2H4)2]2, SnCl2 acetone, AT , 80°C sealed tube, lOh Ipatkin, V.V.; Kovalev, I.P.; Ignatenko, A.V.; Nikishin. G.I. Tetrahedron Lett., 1993, 34, 7971 OTMS OTMS

CO2Me CHO

TrSbCl6, CH£.\2 ,-78°C (>200:1)

76%

Molander. G.A.: Cameron, K.O. J. Org. Chem., 1993, 58, 5931 Me

x.

Y^Y* I

|

Me

AKOCgF^s, toluene 0°C,2h

-,.,",.. Me Ishihara, K.; Hanaki, N.; Yamamoto, H. Synlett, 1993, 127

>99% (86:145:*)

l.KH 2. ZnCl2

SPh

3. MeC(Cl)SPh

Groth. U.: Huhn, T.; Richter, N. Liebigs Ann. Chem., 1993, 49 )H

MeCHO, PhSH , CH£12 SiO2 , it Fuchs, K.; Paquette. L.A. J. Org. Chem., 1994, 59, 528

SPh

Section 365

Ether - Ketone

347

PCWP-H2Q2 EtOH/CH2Cl2 66% ° PCWP = peroxotungstophosphate Sakaguchi, S.; Watase, S.; Katayama, Y.; Sakata, Y.; Nishiyama, Y.: Ishii. Y. J. Org. Chem., 1994, 59, 5681

N-NHCO^t 3. MeOH, H+ 4. H3O+ 5. DBU

77%

Feuerer, A.; Severin. T../. Org. Chem., 1994, 59, 6026 Ph

Ph rn

^^^

SPh

O

SPh

'SPh

TMSO

3 eq. SnCU, -78°C , CH£12

Ph-^

^-^ ^^^ ^ SPh 67%

Hunter. R.: Michael, J.P.; Walter, D.S. Tetrahedron Lett., 1994, 55, 5481

(p-Tol)2S2, cat. Ph2CO, Yb rt,3h

^

»^

"N

82%

'STolyl Taniguchi. Y.: Maruo, M.; Takaki. K.: Fuiiwara. Y. Tetrahedron Lett., 1994, 35, 7789 KF-A12O3, r-BuOOH , CH2C12 MeCN,10min

Ph^ | >^ O

Ph quant

Yadav. V.K.: Kapoor, K.K. Tetrahedron Lett., 1994, 35, 9481

1. NBS , (BzO)2, CCLj, heat

2.1.5 Ag2COs , MeOH, heat De Kimpe. N.: Stanoeva, E.; Boeykens, M. Synthesis, 1994, 427

MeO

-x^

56%

OMe

348

Compendium of Organic Synthetic Methods, Vol 9

Section 365

l.EtCH(OMe)2,TiCL4 CH 2 Cl 2 .-78 0 C,lh

O quant. Hojo, M.; Nagoyoshi, M.; Fujii, A.; Yanagi, T.; Ishibashi, N.; Miura, K.; Hosomi. A. Chem. Lett., 1994, 719

\N/'

>

2 snC!2 , 2 NCS , -10°C

-'

6

80% (40:60 syn:anti) Masuvama. Y.: Kobayashi, Y.; Kurusu, Y. / Chem. Soc. Chem. Commun., 1994, 1123

CO2Me

3eq. 25°C, Ih

PPh3

6 quant.

Wasserman. H.H.: Baldino, C.M.; Coats, SJ. J. Org. Chem., 1995, 60, 8231 O 95%

CH2C12, rt, 2h Straub. T.S. Tetrahedron Lett., 1995, 36, 663

HO

(

Phi, 10% Pd(PPh3)4 , DMF K2CO3,60°C , 18h

Ph

(23:77 cis:trans) Walkup. R.D.: Guan, L.; Kim, Y.S.; Kim, S.W. Tetrahedron Lett., 1995, 36, 3805

Section 365

Ether - Ketone

349

PhI(OAc)2, Mg(ClO4)2, rt , H£), pH 7

99% De Mico. A.: Magarita, R.; Piancatelli. G. Tetrahedron Lett., 1995, 36, 3553

aq. H£>2. hydrotalcite clay MeOH, 72h

66% Cativiela, C.; Figueras, F.; Fraile, J.M.; Garcia, J.I.; Mayoral, J.A. Tetrahedron Lett., 1995, 36, 4125

Mel, 18-crown-6, KOH , reflux, 21h

Ph

T-- QMe

66% Abele, E.; Rubina, K.; Shymanska, M.; Kukevics. E. Svnth. Commun., 1995, 25, 1371

DBU, f-BuOOH DCE, lOh

92% Yadav. V.K.: Kapoor, K.K. Tetrahedron, 1995, 51, 8573 poly-L-leucine catalyst PIT

^>^

^ph

H202-NaOH-CH2Cl2

85% (93% ee) Sanchez, M.E.L.; Roberts, S.M. J. Chem. Soc., Perkin Trans. L, 1995, 1467

350

Compendium of Organic Synthetic Methods, Vol 9

Section 367

1. PhI(OH)OTs 2. PhOH , K2CO2 , dry acetone

ph-

'°Ph

^

67% Prakash. O.: Saini, N.; Sharma, P.K. J. Indian Chem. Soc., 1995, 72, 129

SECTION 366:

ETHER, EPOXIDE, THIOETHER - NITRILE

PTMS [HC(Py)3W(NO)2(CO)][SbF6)2 -»-/ TMS-CN , rt , Ih , MeNO2 Ph Fallen J.W.: Gundersen, L-L. Tetrahedron Lett., 1993, 34, 2275—\ PhCHO

85%

P

Me3SiCH2CN , KF , 90 sec. PhCHO mcrowave

Latouche, R.; Texier-Bonllet. R: Hamelin. J. Bull. Soc. Chim. Fr., 1993, 130, 535 TMSCN , MeCN , 20°C , 1 2h OTMS -*J Ph ^^CN a chemoselective reaction since ketones react very slowly ^ PhCHO

95% Manju, K.; Trehan. S.7. Chem. Soc., Perkin Trans. 1., 1995, 2383

SECTION 367:

ETHER, EPOXIDE, THIOETHER - ALKENE

Enol ethers are found in this section as well as alkenyl ethers. 1. Jones oxidation .OH Bu-

\ -

acetone , 5h reflux

Bu' Majetich. G.: Zhang, Y.; Dreyer, G. Tetrahedron Lett., 1993, 34, 449

:

PhMe2SiH, hexane , O

rt *~ "

/

(

^xV ^

V ft

82%

OSiMe Ph ~OSi 2 84%

Chan. T.H.: Zheng, G.Z. Tetrahedron Lett., 1993, 34, 3095

Section 367

Ether-Alkene

351

O

Pd(PPh3)4, K£O3 , DMF 60°C,1.5h

66% 'OMe Arcadi, A.; Cacchi. S.: Larock. R.C.: Marinelli, F. Tetrahedron Lett., 1993, 34, 2813

Me

^OMe

(xs) ,rt PhCHO

0.5% Yb(fod)3

Y™ OMe

*>

/

OMe

9

Ph' addition of K2CO3 prevents formation of this Deaton, M.V.; Ciufolini. M.A. Tetrahedron Lett., 1993, 34, 2409

TMS.

TMo

1. iBuMgBr, cat. Cp2TiCl2

'TBS

A

»

// //

^\

K ^tf

P. HO HO

CfiHu » D

\\ \V

^C(fi 13

s^^~^

\

OTBS

7Q%

Tani, K.; Sato, Y.; Okamoto, S.; Sato. F. Tetrahedron Lett., 1993, 34, 4977 M

1.0.5M LiClO4, ether 2. IN HC1, THF 15 min, 0°C

OTBDMS

NHBoc

79%

(8:1 threo:erythro) Grieco. P.A : Moher, E.D. Tetrahedron Lett., 1993, 34, 5567 OEt

i . Me2S , TMSOTf , -78°C

2. PhSLi OEt Kim. S.: Park, J.H.; Lee, J.M. Tetrahedron Lett., 1993, 34, 5769

91% SPh

352

Compendium of Organic Synthetic Methods, Vol 9

Section 367

OMe

Me3Si

Mohr. P. Tetrahedron Lett., 1993, 34, 6251 0.1 Pd(OAc)2, CuCl O2, DMF, 24h ». 5eq. CH2=CHPh

I

U

N

85%

Semmelhack. M.F.: Epa, W.R. Tetrahedron Lett., 1993, 34, 7205

>Et F3Cr

,Ph

^SEt

^ Ph

CF?

NaH , rt, 2h

(94:6 Z:E)

H B6gue, J.-P.; Bonnet-Delpon, D.; M'Bida, A. Tetrahedron Lett., 1993, 34, 7753

,OMe TMSOf, iPr2NEt

OMe

^

-20°C->rt,4h

OMe i^^if / U / \

94%

Gassman. P.G.: Burns, S.J.; Pfister, K.B. J. Org. Chem., 1993, 58, 1449

SMe l.catecholborane,3%PdCl2/dppf

U

\

. , reflux

LJL

aq. NaOH, 2h Gridnev, I.D.; Mivaura. N.: Suzuki. A. 7. Org. Chem., 1993, 58, 5351

62%

/SMe

Section 367

Ether - Alkene

1. Me3SixJlx/Cl

353

BF^E^

'

3

,/

2

2. DBU/LiClO4/MeCN , 60°C

C&ii—\/

P'Aniello, F.; Mattii, D.; Taddei. M. Svnlett. 1993, 119 -OH

©

, K2CO3 37%

phCI neat 'CHO ' Billeret, D.; Blondeau, D.; Sliwa. H. Synthesis. 1993, 881

1 . MeOH , HClgas , ether

OMe 52%

MeCN 2. NaOMe , heat

. OMe

Argade. A.B.: Joglekar, B.R. Synth. Commun., 1993, 23, 1979 Mo(CO)s

, PhH, 100°C sealed tube OMe

Harvey. P.P.: Neil, P.A. Tetrahedron, 1993, 49, 2145 H

Q \

/

/

\

OH

Pd2(dba)3-CHCl3,PBu3,1300C Nafion-H perfluorinated resin sulfonic acid , 5h

71%

Ji, J.; Lu. X. J. Chem. Soc. Chem. Commun., 1993, 764

O

NaOCl , Mn(salen) cat. _ ^

>'v. ^ ^K

45%(64%ee)

ether , 4-Ph-pyridine-N-oxide «-1—-O Chang, S.; Heid, R.M.; Jacohsen. E.W. Tetrahedron Lett., 1994, 35, 669 , PhH , 90°C

P

AffiN , sealed tube 2h

65 23% Benati, L.; Capella, L.; Montevecchi. P.C.: Spagnolo, P. J. Org. Chem., 1994, 59, 2818

354

Compendium of Organic Synthetic Methods, Vol 9

Section 367

3 eq. Mg, cat. HgCl2 MeOH, -43°C, 3h »h Lee, G.H.; Choi, E.B.; Lee. E.: Pak. C.S. Tetrahedron Lett., 1994, 35, 2195 ^v \

PbSH, Pd(OAc)2

/

THF,50°C,14h

v

SPh 72%

Backvall. J.-E.: Ericsson, A. J. Org. Chem., 1994, 59, 5850 Jr

CO2Me Ni(CO)4 , MeCN , MeOH

76% (80:20 cis:trans)

Ni(CO)4 , T1O Ac , MeOH 66% (30:70 cis:trans) Delgado. A.: Llebaria, A.; Camps, F.; Moret<5, J.M. Tetrahedron Lett., 1994, 35, 4011

2eq. TMSOTf,CH 2 Cl 2 ,-76°C

A1.W

94% Toshima. K.: Ishizuka, T.; Matsuo, G.; Nakata, M. Tetrahedron Lett., 1994, 35, 5673 Ph

SPh

CuOTf, PhH/THF, 25°C, 0.3 h *-

/sPh =^

SPn

99%

SPh

an alternative to cuBr»Me2S Cohen. T.: Shook, C.; Thiruvazhi, M. Tetrahedron Lett., 1994, 35, 6041 1. Ph2NMnPh , THF 20°C, Ih 2. Me3SiCl, 20°C 30min Cahiez. G.i Figadere, B.; C16ry, P. Tetrahedron Lett., 1994, 35, 6295

OSiMe3

Section 367

Br

BuO

Ether - Alkene

\

^

355

1.2 q. ZnEt2, cat. Ni(acac)2, THF 2.CuCN-2 LiCl

\

==<

"O

J

70%

•Br Vaupel, A.; Knochel. P. Tetrahedron Lett., 1994, 35, 8349

PhSLi, LiCl, Pd(PPh3)4 OTf

^

}

I

SPh

THF, reflux Martfnez. A.G.: Barcina, J.O.; Cerezo, A. de F.; Subramanian, L.R. Synlett, 1994, 561 !.HZrCp2Cl,THF 25°C,lh 76%

Pereira, S.; Zheng, B.; Srehnik. M. J. Org. Chem., 1995, 60, 6260 Cp2TiMe2,THF,65°C PIT

^"^

^OMe

Ph

^^

OMe

67%

Petasis. N.A.: Lu, S.-P. Tetrahedron Lett., 1995, 36, 2393 MMPP, MeOH , rt O

MMPP = monoperoxyphthalate hexahydrate D1 Annibale, A.; Scettri. A. Tetrahedron Lett., 1995, 36, 4659

.OMe

Ph

91 %

TMSCXJL^OTMS

f— OMe

OMe

^

-

Ph.

SnCl2-AcCl, CH^h, 4h 66% Orivama. T.: Ishiwata, A.; Sano, T.; Matsuda, T.; Takahashi, M.; Koga, G. Tetrahedron Lett., 1995, 36, 5581

356

Compendium of Organic Synthetic Methods, Vol 9

Section 368

W(OAr)(OPr)(CHCMe3)Cl(OEt)2 quant. Leconte, M.; Pagano, S.; Mutch, A.; Lefebvre, F.; Basset. J.M. Bull. Soc. Chim. Fr., 1995, 132, 1069 Related Methods:

Section 180A (Protection of Ketones)

SECTION 368:

HALIDE, SULFONATE - HALIDE, SULFONATE

Halocyclopropanations are found in Section 74F (Alkyls from Alkenes). ^r^ •^^^

C13C-CC13 , toluene, 3h ^

.Ph

^^•^^

Cl f f~"L

41%

JL

Ph

RuCl2(PPh)3)3,120°C ^^XX^X^ Sakai. K.: Sugimoto, K.; Shigeizumi, S.; Kondo, K. Tetrahedron Lett., 1994, 35, 737 l.C!2,NF3OEt2

,.OH

/ /

V Cl V 82%

2. HC1

Tordeux, M.; Boumizane, K.; Wakselman. C. J. Org. Chem., 1993, 58, 1939

:NOH

NO+BF4-, PPHF

PPHF = pyridinium polyhydrogen fluoride York, C.; Prakash, G.K.S.; Wang, Q.; Qlah. G.A. Svnlett. 1994, 425 , Me3SiBr CH2C12,0°C

'Br Hazra. E.G.: Chordia, M.D.; Bahule, B.B.; Pore, V.S.; Basu, S. J. Chem. Soc., Perkin Trans. L, 1994, 1667

.

X^I ( _L P Ph \ Cl I (6 : 1) 94% Zefirov. N.S.: Sereda, G.A.; Sosonuk, S.E.; Zyk, N.V.; Likhomanova, T.I. Synthesis, 1995, 1359 jf *

KIC12,H2Q

^

Ph

Section 369

Halide - Ketone

SECTION 369:

357

HALIDE, SULFONATE - KETONE O

O

Cl

I C02Et

hexane.rt

^*S Y

\ C1

92%

CO2Et de Faria, A.R.; Matos, C.R.; Correia. C.R.D. Tetrahedron Lett., 1993, 34, 27 NBS , aq. MeCN , cat. HC1

r

^

h

"

"

BF

81% Morton. H.E.: Leanna, M.R. Tetrahedron Lett., 1993, 34, 4481 1. C1CH2I, MeLi, -78°C 2. Me3SiCl, -78°C -» rt *OEt

Br Br Barluenga. J.: Pedregal, B.; Concell6n, J.M. Tetrahedron Lett., 1993, 34, 4563 HTIB , I2 , MeCN, rt; reflux, 20h

HTIB = hydroxy p-tosyloxyiodo benzene Bovonsombat, P.; McNeils. E. Tetrahedron, 1993, 49, 1525 1. pyridinium polyhydrogen fluoride CH2C12 2. PW(02CCF3)2

61% Karam, O.; Jacquesv. J.-C.: Jouannetaud, M.-P. Tetrahedron Lett., 1994, 35, 2541 1. PhCHO , 5% (BiCl3-l.5 ZnCl2)

Ph

\^\^Ph

TMSO' 2.Me3SiCl o C1 Le Roux, C.; Gaspard-Iloughmane, H.; Dubac. J. /. Org. Chem., 1994, 59, 2238

83%

358

Compendium of Organic Synthetic Methods, Vol 9

Section 369

1.2 LDA, THF-HMPA, -78°C 2.CgHnCHO

o

»

Ph/Sx-^F 3.FVP(508°C) C^-f Reutrakul. V.: Kruahong, T.; Pohmakotr, M. Tetrahedron Lett., 1994, 35, 4853

82x4g%

PDC, I 2 , CH2C12 it, overnight

49% conversion Bovonsombat, P.; Angara, G.J.; McNeils. E. Tetrahedron Lett., 1994, 35, 6787

NBS , /-BuOH , 30°C 1.5h

Jl

54%

j Furet, N. Tetrahedron Lett., 1995, 36, 3691

O-

/ x

1. HZrCp2Cl 2. AcCl, 15% CuBfSMe2

3. NBS 93%

6

Zheng, B.; Srebnik. M. Tetrahedron Lett., 1995, 36, 5665 Q

poly(4-methyl-5-vinylthiozolium) hydrotribromide

II N

quant.

h^\ 1.5h Babadjamian. A.: Kessat, A. Synth. Commun., 1995, 25, 2203

Qy ^\S\ y\\

/

u >Jntt**An

Cl

2.2eq. 2 FeCl-3, DMF

Booker-Milburn. K.I.: Thompson, D.F. J. Chem. Soc., Perkin Trans. 1., 1995, 2315

51%

Section 371

Halide - Nitrile

359

_ .o

DMSO, (COC1)2, MeOH O

NEt3,CH2Cl2,-60°C Raina, S.; Singh. V.K. Tetrahedron, 1995, 51, 2467 , 10-15°C , 2h

F 70% Chambers, R.D.; Greenhall, M.P.; Hutchinson, J. J. Chem. Soc. Chem. Commun., 1995, 21

SECTION 370:

HALIDE, SULFONATE - NITRILE NO ADDITIONAL FJCAMPLES

SECTION 371:

HALIDE, SULFONATE - ALKENE l.LDA 2.ClP(0)(OEt)2 °

-"

3.TMS-I

Lee, K.; Wiemer. P.P. Tetrahedron Lett., 1993, 34, 2433 SiMe2f-Bu

Br

LDA , ether -78°C -> rt

Br Shinokubo, H.; Oshima. K.: Utimoto. K. Tetrahedron Lett., 1993, 34, 4985 )H

'

"

'

1. C13CCN 2.I2,K2CO3,ether

76% x 88%

C7H15 (33 : Friesen. R.W.: Giroux, A.; Cook, K.L. Tetrahedron Lett., 1993, 34, 5983

1)

:ci3

360

Compendium of Organic Synthetic Methods, Vol 9

r

Section 372

TMSCl, Nal, MeCN

Me

x

H20,25°C

< XX

85%

Luo. F -T •. Kumar, K.A.; Hsieh, L.-C.; Wang, R.-T. Tetrahedron Lett., 1994, 35, 2553

cat. Pd(OAc)2 , LiCl Cl% benzoquinone, 20°C \ AcOH-acetone 46% Backvall. J.-E.: Nilsson, Y.I.M.; Andersson, P.G.; Gatti, R.G.P.; Wu, J. Tetrahedron Lett., 1994, 35, 5713

I 2 , CAN, MeCN, 5h reflux

O

55% (67/33 dl/meso) Horiuchi. C.A.: Takahashi, E. Bull. Chem. Soc. Jpn., 1994, 67, 271 u

SiMe3

IPy2BF4/2HBF4 , CH2C12

C6H13

j

77% Barluenga. J.: Alvarez-Garcfa, L.J.; Gonzalex, J.M. Tetrahedron Lett., 1995, 36, 2153

1.IC1,CH2C12,-78°C reversing order of addition leads to 38% of Z-iodoalkene Stewart, S.K.; Whiting. A. Tetrahedron Lett., 1995, 36, 3929

SECTION 372:

CHO

KETONE - KETONE Acp,CoCl2 MeCN

O 15% 61% Bhatia, B.; Punniyamurthy, T.; Iqhal. J. J. Org. Chem., 1993, 58, 5518

3

Section 372

Ketone - Ketone

2 PhLi, THF, 20°C

M^-N

N-Me

361

^.

30min

V-/

D.

"u>

"Ph

^

«%

O

Mueller-Westerhoff. U.T.: Zhou, M. Tetrahedron Lett., 1993, 34, 571

O

2

Pn

Ph—MgBr THF , -70°C O

Mitchell. R H.: Iyer, V.S. Tetrahedron Lett., 1993, 34, 3683 )Bn

^X^OTMS I^Jf , Fe2(CO)9 CO, ether, 2h 0

^^

81%

Zhou, T.; Green. J.R. Tetrahedron Lett., 1993, 34, 4497

80% Ph' Iwasawa, N.; Hayakawa, S.; Funahashi, M.; Isobe, K.: Narasaka. K. Bull. Chem. Soc. Jpn., 1993, 66, 819

C8H17

9 Cl

C8H,

•ci O

A1C12, CS2

Mohr, B.; Enkelmann, V.: Wegner. G. 7 Org. Chem., 1994, 59, 635

362

Compendium of Organic Synthetic Methods, Vol 9

Section 373

^ OTMS BF3OEt2 Jenkins, T.J.; Bumell. D.J. J. Org. Chem., 1994, 59, 1485 O

O

Yb-TMS-Br THF, reflux

<

I

/

68%

\

Taniguchi. Y.: Nakahashi, M.; Kuno, T.; Tsuno, M.; Makioka, Y.; Takaki. K.: Fuiiwara. Y. Tetrahedron Lett., 1994, 35, 4111 OAc

AA

pr

„

Ph'

.

^•^

.

CoC,2

Maikap, G.C.; Reddy, M.M.; Mukhopadhyay, M.; Bhatia, B.; IqhaLL Tetrahedron, 1994, 50, 9145

)H PCWP, DCE, reflux, 3h

Bu

U

H

OH PCP = [p-C5H5N(CH2)i5Me]3 {PO4[W(O)(O2)2)t} O 93% Iwahama, T.; Sakaguchi, S.; Nishiyama, Y.; Ishii. Y. Tetrahedron Lett., 1995, 36, 1523 REVIEW: "a-Diones from Cyclic Oxamides and Organolithium Reagents: A New, General and Environmentally Beneficial Synthetic Method," Mueller-Westerhoff. U.T.: Zhou, M. Synlett, 1994, 975

SECTION 373:

KETONE - NITRILE

--V CN

, DCE, 70°C

20% Pd(OAc)2-PPh3-dppb 65h Nozaki, K.; Sato, N.; Takava. H. 7. Org. Chem., 1994, 59, 2679

Ph O

74%

Section 374

Ketone - Alkene

SECTION 374:

363

KETONE - ALKENE

For the oxidation of allylic alcohols to alkene ketones, see Section 168 (Ketones from Alcohols and Phenols) For the oxidation of allylic methylene groups (C=C-CH2 —> C=C-C=O), see Section 170 (Ketones from Alkyls and Methylenes). For the alkylation of alkene ketones, also see Section 177 (Ketones from Ketones) and for conjugate alkylations see Section 74E (Alkyls form Alkenes).

MeO2C Me PdCl2(PhCN)2,50°C °2C SnCl2, MeCN, 33h Masuvama. Y.: Sakai, T.; Kurusu, Y. Tetrahedron Lett., 1993, 34, 653

OC02Me

NO2

SnCl2-2 H 2 O, rt THF,6h 80%

Das, N.B.; Sarma, J.C.; Sharma. R.P.: Bordoloi, M. Tetrahedron Lett., 1993, 34, 869

S^^

XX

^X\SnBu,

X^X

AIBN

XX

Br

k

^

Kraus. G.A.: Andersh, B.; Su, Q.; Shi, J. Tetrahedron Lett., 1993, 34, 1741

=Cr(CO)5 l

Ph

=

Ph

' MeO 50°C , 3h , Si02

2.CAN,0.1Maq. HNO3

rt, 20 min

II

II

Harrity, J.P.A.; Kerr. W.J.: Middlemiss, D. Tetrahedron Lett., 1993, 34, 2995

'Ph

364

Compendium of Organic Synthetic Methods, Vol 9

C02Et

I

Section 374

I. PhH , Cu(OAc)2 Pb(OAc)4,2d 2. ethylene glycol, CH2C12

Schultz, A.G.; Holoboski, M.A. Tetrahedron Lett., 1993, 34, 3021

i~ ^MHBB^-^/.

51%

MTO, CH^l;,, rt

J^_

\

MTO = methyltrioxorhenium Junga, H.; Blechert S. Tetrahedron Lett., 1993, 34, 3731

Ph

^=^*\

'-

Mo(CO)6, DMSO, Toluene 100°C, 12h

\^^/ Jeong. N.: Lee, S.J.; Lee, B.Y.; Chung, Y.K. Tetrahedron Lett., 1993, 34, 4027

O21 .Br

/—V

O

SmI3, THF, rt, 2h (mostly E)

Yu, Y.; Lin, R.; Zhang. Y. Tetrahedron Lett., 1993, 34, 4547

CHC13 , rt, 8h

TBDMS O Konopelski. J.P.: Kasar, R.A. Tetrahedron Lett., 1993, 34, 4587

65%

Section 374

Ketone - Alkene

365

O Rawal. V.H.: Zhong, H.M. Tetrahedron Lett., 1993, 34, 5197

JL

EL

0.01PdCl2(MeCN)2,20°C \ 75% DMF, 2h OEt Parrain, J.-L.; Beaudet, I.; Duchene, A.; Watrelot, S.; Quintard, J.-P. Tetrahedron Lett., 1993, 34, 5445 A {? II

© 0 >=NMe2 CF3CO2

88%

h r \ CH2C12 , reflux , 96h Ales, C.; Janousek, Z.; Viehe. H.G. Tetrahedron Lett., 1993, 34, 5711

1. BuMgBr , 10% Cul , TMSC1 HMPA , THF , -78°C 2. CH2I2 , 2 eq. Et2Zn 3. 2.2 eq. FeCl3, DMF, 0°C , , 4.NaOAc,MeOH ^^ Booker-Milburn. K.I.: Thompson, D.F. Tetrahedron Lett., 1993, 34, 7291 TMS

KJ \^^

99x93x54%

BuaSnH, AIBN PhH slow addition

f

"

"™S

(7:3 Z:E) 81% fast addition

(2:1 Z:E) 70% Sha. C.-K.: Shen, C.-Y.; Jean, T.-S.; Chiu, R.-T.; Tseng, W.-H. Tetrahedron Lett., 1993, 34, 7641

366

Compendium of Organic Synthetic Methods, Vol 9

J/

Section 374

Rh(H) octanoate, 25°C CH2C12

97%

6 Padwa. A.: Kassir, J.M.; Semones, M.A.; Weingarten, M.D. Tetrahedron Lett., 1993, 34, 7853

NO2 , DMF

/

\\

85%

2.5 Pdz(dba)3, 50% Cul SnBus O

O

Liebeskind. L.S.: Riesinger, S.W. J. Org. Chem., 1993, 58, 408

Pd2(dba)3-CHCl3 PPh3 , LiCl THF.HP 70°C (73

:

\

27) 67%

Ihle, N.C.: Heathcock. C.H. J. Org. Chem., 1993, 58, 560

EtO^C

=

Bu

Et02C — CuBr-SMe2 , HMPA TMSC1

. „ ^-

65%

Bu Crimmins. M.T.: Nantennet, P.O.; Trotter, B.W.; Vallin, I.M.; Watson, P.S.; McKerlie, L.A.; Reinhold, T.L.; Cheung, A.W.; Stetson, K.A.; Dedopoulou, D.; Gray, J.L. / Org. Chem., 1993, 58, 1038

Section 374

Ketone - Alkene

367

I. KH,

=

-^ 2. 2 eq. CuSO4 , 1 10°C

0

=0

53%

Trost. B.M.: Parquette, J.R. J. Org. Chem., 1993, 58, 1579 v

C02(CO)8, MeCN rt -> 75°C -

\

Me

/^^^\ :O

Hove. T.R.: Suriano, J.A. J. Org. Chem., 1993, 58, 1659

O

2 eq. PhCHO , ZrOCl2-8 H2O * "n

^er\o/~<

Ph Yuki, T.; Hashimoto, M.; Nishiyama, Y.; Ishii. Y. J. Org. Chem., 1993, 58, 4497

Ph 5% Pd(OAc)2 ,4 NaOAc 100°C , DMF , BU4NC1

1

Larock. R.C.: Doty, M.J.; Cacchi, S. /. Org. Chem., 1993, 58, 4579 O

W(CO)6, THF, CO, sealed tube Bu

hv,65°C -> 110°C

Bu

\^^\ ^/

I

/\^^^y

/=O 57%

Hove. T.R.: Suriano, J.A. J. Am. Chem. Soc., 1993, 115, 1154

368

Compendium of Organic Synthetic Methods, Vol 9

PhOCH, SnCl4-NBu3

*-

Section 374

\ ^v^ ^?x

Ph

85% (20:1 E:Z) ' Yamaguchi. M.: Hayashi. A.: Hirama, M. 7. Am. Chem. Soc., 1993, 115, 3362

5% RhCl(PPh3)3, toluene, 120°C Ph^^

Huffman, M.A.; Liebeskind. L.S. J. Am. Chem. Soc., 1993, 115, 4895 P

Me3SiCN

n

Ph

^=

'

\

Cp2Ti(PMes)2

o

Berk, S.C.; Grossman, R.B.; Buchwald. S.L. 7. Am. Chem. Soc., 1993, 115, 4912 CO2Me

CO, 10% Pd(OAc)2-dppp PhH-MeCN-MeOH

\^X^V « O

fil

a,

81/0

Mandai. T.: Tsuji, J.; Tsujiguchi, Y.; Saito. S. 7. Am. Chem. Soc., 1993, 115, 5865

OMe

Funk. R.L.: Fitzgerald, J.F.; Olmstead, T.A.; Para, K.S.; Wos, J.A. 7. Am. Chem. Soc., 1993, 115, 8849

Section 374

Ketone - Alkene

369

, 10% (cod)CpRuCl OH

20% NH4PF6, neat, 100°C 45%

Bu

Bu

Bu Trost. B.M.: Martinez, J.A.; Kulawiec, R.J.; Indolese, A.F. J. Am. Chem. Soc., 1993, 115, 10402

PhCHO, SnCl2, Na2SO3

X^^X^

.Br PIT ^^