Compendium of Organic Synthetic Methods Volume 5

Compendium of Organic Synthetic Methods Compendium of Organic Synthetic Methods Volume 5 LEROY G. WADE, Jr. DEPARTMEN...

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Compendium of Organic Synthetic Methods

Compendium of Organic Synthetic Methods Volume 5 LEROY G. WADE, Jr. DEPARTMENT OF CHEMISTRY COLORADO STATE UNIVERSITY FORT COLLINS, COLORADO

A Wiley-lnterscience Publication

JOHN WlLEY & SONS New York

0

Chichester

0

Brisbane

0

Toronto

0

Singapore

A NOTE TO THE READER This book has been electronically reproduced om digital information stored at John Wiley & Sons, Inc. We are pleased that the use of this new technology Will enable us to keep works of enduring scholarly value in print as long as there is a reasonable demand for them. The content of this book is identical to previous printings.

Copyright @ 1984 by John Wiley & Sons, Inc. All

rights reserved. Published simultaneously in Canada.

iio 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. Danvers. MA 01923, (978) 750-8400, fax (978) 750-4470. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 R i w Street, Hoboken, NJ 07030. (101) 748-6011, fax (201) 748-6008. E-Mail: PERhlREQ@\VILEY.COIvl.

To order books or for customer service please; call 1(800)-CALL-WILEY (225-594s).

Library of Congress Catalog Card Number: 71 - 162800 ISBN 0-471-86728-4 18 17 16 15 14

PREFACE By their compilation of Volumes 1 and 2 of this Compendium, Ian and Shuyen Harrison filled one of the greatest needs of the synthetic community: a method for rapidly retrieving needed information from the literature by reaction type rather than by the author's name or publication date. Compendium of Organic Synthetic Methods, Volume 5, presents the functional group transformations and difunctional compound preparations of 1980, 1981, and 1982. We have attempted to follow as closely as possible the classification schemes of the first three volumes; the experienced user of the Compendium will require no additional instructions on the use of this volume. Perhaps it is fitting here to echo the Harrison's request stated in Volume 2 of the Compendium: The synthetic literature would become easily accessible and more useful if chemists could write well-organized, concise papers with charts and diagrams that allow the reader to assess quickly and easily the scope of the published research. In addition, the reporting of actual, isolated yields and detailed experimental conditions will save a great deal of wasted effort on the part of other chemists hoping to apply the reported reactions to their own synthetic problems. I wish to express my gratitude to the many people who helped to bring this book to completion: To Mrs. Rosalie Jaramillo for her patience and dedication in the preparation of the camera-ready copy; to Dr. James McKearin, Dr. Forrest Sheffy, and Ron Wilde for proofreading the manuscript with great care and offering hundreds of helpful suggestions; and to my wife Betsy for her patience, help and moral support throughout the preparation of this Compendium. Fort Collins, Colorado November 1983

LEROYG. WADE,JR.

CONTENTS ABBREVIATIONS

ix

INDEX, MONOFUNCTIONAL COMPOUNDS

xi

INDEX, DIFUNCTIONAL COMPOUNDS

xii

INTRODUCTION

xiii

1 PREPARATION

OF ACETYLENES

i

2 PREPARATION OF CARBOXYLIC ACIDS, ACID HALIDES,

AND ANHYDRIDES

9

3 PREPARATION OF ALCOHOLS AND PHENOLS

24

4 PREPARATION OF ALDEHYDES

92

5 PREPARATION OF ALKYLS, METHYLENES, AND ARYLS

124

6 PREPARATION OF AMIDES

168

7 PREPARATION OF AMINES

191

8 PREPARATION OF ESTERS

224

9 PREPARATION

OF ETHERS AND EPOXIDES

256

10 PREPARATION OF HALIDES AND SULFONATES

272

11 PREPARATION OF HYDRIDES

289

12 PREPARATION OF KETONES

304

13 PREPARATION OF NITRILES

353

14 PREPARATION OF OLEFINS

366

15 PREPARATION OF DIFUNCTIONAL COMPOUNDS

400

vii

ABBREVIATIONS An attempt has been made to use only abbreviations whose meaning will be readily apparent to the reader. Some of those more commonly used are the following: Ac AIBN Am Ar 9-BBN BOC (t-BOc) Bu Bz CP DBU DCC DDQ DEAD DIBAL (DIBAH) DMAD DME DMF DMSO ee Et Hex HMPA, HMPT hv

L

LAH LDA MCPBA Me MEM Ms MTM MVK NBS

Acetyl Azobisisobutyronitrile Amy1 Aryl 9-borabicyclo[3.31lnonane t-Butyloxycarbonyl Butyl Benzyl Cyclopentadienyl 1,5-diazabicyclo[5.4.O]undecene-5 Dicyclohexylcarbodiimide 2,3-Dichloro-5,6-dicyanobenzoquinone Diethyl azodicarboxylate Diisobutylaluminum hydride Dimethyl acetylenedicarboxylate 1,2-Dimethoxyethane Dimethylformamide Dimethyl sulfoxide Enantiomeric excess Ethyl Hexyl Hexamethylphosphoramide (hexamethylphosphoric triamide) Irradiation with light Triphenylphosphine ligand (if not specified) Lithium aluminum hydride Lithium diisopropylamide rneta-Chloroperbenzoic acid Methyl p-Methoxyethoxymethyl Methanesulfonyl Methylthiomethyl Methyl vinyl ketone N-bromosuccinimide IX

X

Ni

8 PCC Ph PPA PPE

Pr PTC PY, Pyr RT Sia Tf TFA TFAA THF TH P TMEDA TMP TMS To1 Ts Z A

ABBREVlATlONS

Raney nickel Polymeric backbone Pyridinium chlorochromate Phenyl Polyphosphoric acid Polyphosphate ester Propyl Phase-transfer catalysis Pyridine Room temperature secondary-isoamyl Trifluoromethane sulfonate Trifluoroacetic acid Trifluoroacetic anhydride Tetrahydrofuran Tetrahydropyranyl Tetrarnethylethylenediamine 2,2,6,6-Tetramethylpiperidine Trimethylsilyl Tolyl p-Toluenesulfonyl BenzyloxycarbonyI Heat

27 19

12 6

29 19

30 20

14 8

15 8

Miscellaneous compounds

28 19

25 17 26 18

Olefins

Nitriles

Ketones

Hydrides (RH)

Halides. sulfonates. sulfates

10 4

~~

44 75

42 52

40 48 41 49

60 118

59 117

58 116

57 114

55 109 56 112

~

75 166

74 149

73 149

72 145

70 130 71 141

69 129

39 41

Ethers, epoxides

54 108

68 128

38 38

23 15

Esters

Amines

52 105

65 127

50 104 36 37 37 37

34 25

21 14 22 15

~~

19 12

63 125 64 126

62 125

61 124

48 96 49 103

47 93

46 92

Amides

Alkyls. rnethylenes. aryls

Aldehydes

4 2

33 25

18 11

Alcohols, phenols

32 24

17 9

2 2

~~

31 24

Carboxylic acids, acid halides. anhydrides

~

16 9

1 1

Acetylenes

Sections- heavy type Pages- light type

90 189

89 188

88 187

87 186

85 184 86 185

84 184

83 183

81 177 82 180

78 175 79 176

77 168

105 212

104 209

103 208

102 204

100 200 101 203

96 195 97 196

93 191 94 192

119 254

118 253

117 251

115 245 116 247

114 243

113 240

111 239

135 271

134 266

132 265

130 263 131 264

129 263

128 261

124 260

123 256

108 233 109 237

122 256

107 225

106 224

150 287

149 285

147 284

145 279 146 280

144 278

143 278

142 276

140 275

138 273

137 272

136 272

165 302

163 301

160 295

159 294

158 293

157 293

155 292

168 310

153 290

180 341

179 339

178 337

177 329

175 325 176 327

174 324

173 322

172 321

170 319

169 318

167 306

152 289

166 304

207 389

205 382 206 388

204 380

203 379

210 395

194 209 364 394

193 363

192 362

190 359 191 361

186 358 187 358

20a 375 201 378 202 379

199 371

198 36s

183 354 184 354

197 36E

182 353

1% 36E

INDEX. MONOFUNCTIONAL COMPOUNDS

30A 45A 60A 9OA 105A 120A 180A 210A

20 79 119 190 216 255 343 398

Sect. Pg.

Blanks in the table correspond to sections for which no additional examples were found in the literature.

Carboxylic acids Alcohols, phenols Aldehydes Amides Amines Esters Ketones Olefins

1 PROTECTION I

INDEX, DIFUNCTIONAL COMPOUNDS Sections- heavy type P,ages- light type

301 400 302

312 409 313

323 324

315

427 325

412 316

41 2 -

327

336

344

351

357 /

403

-

404

319 414

329 438

338 458

309 404 310 406

320 416 321 417

330 439 331 449

339 460 340 462

311 407

322 419

332 450

341 462

/

476

483

497

503

347 470

354 476 355 478

360 486 361 491

369 506

372 516

349 472

356 478

362 491

365 498 366 500 367 501

371 511

374 525

376 540

377 543

Blanks in the table correspond to sections for which no additional examples were found in the literature.

xii

INTRODUCTION Relationship between Volume 5 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 5 presents over 1000 examples of published methods for the preparation of monofunctional compounds, updating the 6000 in Volumes 1 through 4. In addition, Volume 5 contains over 1000 additional examples of preparations of difunctional compounds and various functional groups, updating the sections introduced in Volume 2. The same systems of section and chapter numbering are used in all five volumes. 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 listed in a somewhat arbitrary order, although an effort has been made to put similar reactions together when possible. 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 t-BuOH +. t-BuCOOH, PhCH,OH + PhCOOH and PhCH=CHCH&H + PhCH=CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Conjugate reduction and alkylation of unsaturated ketones, aldehydes, esters, acids, and nitriles have been placed in category 74, Alkyls from Olefins. The terms hydrides, alkyls, and aryls classify compounds containing reacting hydrogens, alkyl groups, and aryl groups, respectively; for example, RCH,-H + RCH,COOH (carboxylic acids from hydrides), RMe +. RCOOH (carboxylic acids from alkyls), RPh + RCOOH (carboxylic acids from aryls). Note the distinction between RzCO.+ R2CH2(methylenes from ketones) and RCOR’ +. RH (hydrides from ketones). Alkylations involving additions across double bonds are found in section 74, Alkyls from Olefins.

xiii

xiv

INTRODUCTION

The following examples illustrate the classification of some potentially confusing cases: RCH=CHCOOH += RCH =CH2 RCH=CHp + RCH=CHCOOH ArH + ArCOOH ArH + ArOAc RCHO+ RH RCH=CHCHO + RCH=CH2 RCHO + RCH3 R&H, + R2C0 RCH,COR + R2CHCOR RCH=CH2 + RCH2CH3 RBr+RC=CH += RC=CR ROH+RCOOH + RCOOR RCH=CHCHO -+ R2CHCH2CH0 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 olefins) (acetylenes from halides; also (acetylenes from acetylenes) (esters from alcohols; also esters from carboxylic acids) (alkyls from olefins) (alkyls from olefins)

How to Use the Book to Locate Examples of the Preparation or Protection of Monofunctional Compounds. Examples of the preparation of one functional group from another are located via the monofunctional index on p. xi, which lists the corresponding section and page. Thus Section 1 contains examples of the preparation of acetylenes from other acetylenes; Section 2, acetylenes from carboxylic acids; and so forth. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of the index. Thus Section 1 gives examples of the reactions of acetylenes that form other acetylenes; Section 16, reactions of acetylenes that form carboxylic acids; and Section 31, reactions of acetylenes 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 acetylenes from acetylenes, carboxylic acids from carboxylic acids, and alcohols and phenols from alcohols and phenols. Alkylations which involve conjugate additions across a double bond are found in section 74, Alkyls from Olefins. 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 on olefins from aldehydes and Section 207 on olefins from ketones.

INTRODUCTION

xv

Examples of the protection of acetylenes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and olefins are also indexed on p. xi. The pairs of functional groups alcohol, ester, carboxylic acid, ester; amine, amide; 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, of course, also be consulted on the text. The original literature must be used to determine the generality of reactions. A reaction given in this book for a primary aliphatic substrate may also be applicable to tertiary or aromatic compounds. This book does not attempt to provide experimental conditions or precautions, under the assumption that the reader will study the original literature before attempting a reaction. Not to do so would be hazardous, as well as foolish. The original papers usually yield a further set of references to previous work. Subsequent publications can be found by consulting 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, aldehyde, amide, amine, ester, ether, epoxide, halide, ketone, nitrile, and olefin. Reactions that form difunctional compounds are classified into sections on the basis of the two functional groups of the product. The relative positions of the groups do not affect the classification. Thus preparations of 1,2-aminoalcohols, 1,3aminoalcohols and 1,4-aminoalcohols are included in a single section. The following examples illustrate the application of this classification system: Difunctional Product

Section Title

RC=C-C=CR RCH(0H)COOH RCH=CHOMe RCHF, RCH( Br)CH,F RCH(0Ac)CH*OH RCH(0H)COOMe RCH=CHCH,COOMe RCH=CHOAc

Acetylene - Acetylene Carboxylic Acid - Alcohol Ether-Olefin Halide - Halide Halide - Halide Alcohol - Ester Alcohol - Ester Ester - Olefin Ester-Olefin

How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on p. xii gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol - Ester) contains examples of the preparation of hydroxyesters;

xvi

INTRODUCTION

Section 323 (Alcohol -Alcohol) contains examples of the preparation of diols. Some preparations of olefinic and acetylenic compounds from olefinic and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, RCH=CHBr + RCH=CHCOOH, Carboxylic acids from Halides (monofunctional sections) or Carboxylic acid- Olefin (difunctional sections). 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. Many literature preparations of difunctional compounds are extensions of the methods applicable to monofunctional compounds. Thus the reaction RCI + ROH can clearly be extended to the preparation of diols by using the corresponding dichloro compound as a starting material. Such methods are not fully covered in the difunctional sections. 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 RCH(OAc)CH,OAc (Ester- Ester) would thus be of interest to anyone preparing the diol RCH(OH)CH20H(Alcohol - Alcohol).

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 1 PREPARATION OF ACETYLENES Sect ion 1 Acetylenes from Acetylenes

PdC12, C u C l

C5H1 -CrCH

NaOAc, MeOH

, co * C5H,, -CzC-CO2Me

74%

Tetr Lett, 2 1 , 849 (1980)

0

HCc C-C ( CH3 )

1

CO2

(Cqj

Tetr Lett, 2-l,

1595 (1980)

2

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 2

Section 2 Acetylenes from Acid D e r i v a t i v e s P h - CZ CH t

CuI, E t 3 N w

Ph-CeC-2,

81 %

t o 1 uene

0

B u l l . Acad. USSR Chem.

30, 918

(1981)

S e c t i o n 3 A c e t y l e n e s f r o m A1 coho1 s No a d d i t i o n a l examples

S e c t i o n 4 A c e t y l enes f r o m A1 dehydes

CHO

C-CH

79%

OM e

OM e

Tetr Lett,

-hP

\

CHO

21,

4021 ( 1 9 8 0 )

-7 Fr

CHSnBu3

Ph

40% Tetr Lett,

23,

4607 ( 1 9 8 2 )

SECTION 4

1 ) PPh3, C B r 4 Hx-CHO

2) BuLi

1

CH2CH2-CH0 @THP

1

ACETYLENES FROM ALDEHYDES

'

2)) BH3*THF Ph3P=CH2

Hx-C=C-Li

~

3

ElirH2)t/ Chem Ber,

Hx-C:C-(

115,028

71 %

(1982)

s S e c t i o n 5 Acetylenes from A1 k y l s , Methyl enes, and Aryl No examoles S e c t i o n 6 Acetylenes from Amides No a d d i t i o n a l exampl es S e c t i o n 7 Acetylenes f r o m Amines

No a d d i t i o n a l examples S e c t i o n 8 Acetylenes from E s t e r s

No a d d i t i o n a l examples S e c t i o n 9 Acetylenes from H a l i d e s No examples

CH2)4-OTHP

4

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 10

S e c t i o n 10 Acetylenes from Halides

ur

KS OCMe3

44,By

18-crown-6 -

-

0, 83%

Liebigs A n n . Chern, 1 (1980)

KO H

Hx-CH-CH2

I I Br Br

I,

95%

Hx-CZCH

P.T.C.

37, 1653

( 1 981 )

H-C=C-CH(OEt)2

67%

Tetrahedron , + -

Bu4N OH

-

H20, nentane

Crg Syn, 5 9 , 10 (1980) 1 ) BuLi

Hx-CH=CF2

c1

2 ) LDA

* Hx-CZC-BU Chem L e t t , 935 (1380)

Chem L e t t , 669 (1980)

68%

SECTION 10

ACETYLENES FROM H A L I D E S

5

I( CH2)9COOH HMPA

t

+

H Cz C ( CH2 ) 9COOH

96%

Li C:CH .EDA S y n t h Comm, I @ , 6 5 3 (1980)

Bu-CzC-Li t

2 ) H30@

B r ( CH2)8@-THP

55%

BU-C-C-(CH~)&IH

JOC (USSR),

16,1 7 2 8

JOC

17,18

(1980)

P h C- C - S nMe3 t

02N

(USSR),

1 ) 2 HC-C-TMS

L2PdC12, CuI

2) -OH, H 2 0

Br Me

(1981)

++

C-CH

HC-C

S y n t h e s i s , 627 (1980)

%80%

6

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

Me3Si -CzC-SiMe 3

1 ) P h B r , A1C13 2 ) L-BuCl, A 1 C 1 3

SECTION 10

Ph-CEC-t-Bu

86%

JCS Chem Comm, 959 (1982) Section 11 Acetylenes from Hydrides

no examples For examples o f the reaction RC-CH (Acetylene - Acetylene)

-).

RCrC-C:CR'

see section 300

Section 12 Acetylenes from Ketones

1 ) LDA

C- CH

2 ) ClPO(OEt)* 3 ) LDA 4 ) H3@ JOC,

8

0II Ph-C-CH2-C-CH3

5, 2526

-

(1980)

KF, Et2NCF2CHFCF3

Ph-CSC-

Chem L e t t , 1327 (1980)

72%

SECTION 12

ACETYLENES FROM KETONES

7

c I

Synthesis, 285 (1981)

OMe

1 ) H2C=C=CHTMS, T i C1 2 ) KF,

Me2S0

JOC, 45, 3925 (1980)

Et-C- C-L i

+

89%

1 ) THF 2 ) CH31, THF/DMSO

Synthesis, 459 (1981) Section 13 Acetylenes from Nitriles no examples

CEC-H

92%

8

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

Section 14 Acetylenes from Olefins

SECTION 14

OMe Tetr Lett, 2_?_, 2301 (1981) Section 15 Acetylenes from Miscellaneous Compounds Review:

"Heterocyclic Rearrangements: New Cumul enes and Acetylenes" Bull SOC Chim Belqes, 91,997 (1982)

Section 15A Protection of Acetylenes no additional examples

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 2 PREPARATION OF CARBOXYLIC ACIDS, ACID HALIDES, AND ANHYDRIDES S e c t i o n 16 C a r b o x y l i c A c i d s from Acetylenes CH3 ( CH2) 5 - C ~ C H

PhIO

C ( C HH ~ )~~ - C O O H

~

RuC1 2L3

H e l v Chim Acta,

Hd

81 %

64,2531

(1981)

H20Me

H2N-CH2-C-CH

-CH ( OMe)

2) s i m i l a r , using BzBrC

,,XCH3 COOH

H2N

3 ) CH31 4 ) several steps Angew Chem I n t Ed,

63% 84%ee

19,725

(1980)

S e c t i o n 17 C a r b o x y l i c Acids f r o m A c i d H a l i d e s from Carboxyl ic Acids

PhCH2CH2COOH

P h3 P Br2 CH,Cl,

PhCH2CH2C-Br

S y n t h e s i s , 684 (1982)

84%

10

COMPENDIUM

n it CH3-C-C-OH 00

OF O R G A N I C SYNTHETIC METHODS V O L 5 00 It II

CH30CHC1

bCH3-C-C-Cl Org Syn,

0

II

n-C7H, 5 C - C l

0

He3SiBr

*

CH3-C-Br

9 1yme

50%

61,1

(1983)

0 I1

93 s

n-C7H1 5 C - B r

-

w

(CF3 )$d

It

SECTION 17

S y n t h e s i s , 216 ( 1 9 8 1 )

CH3-C-F

95%

JCS Chem Comm, 670 (1980)

Me C

0 It ,c-c1

2NaI

‘c-c1

CH3CN

I1

0 It Me2C<

0

c-I

90%

E- I

0

S y n t h e s i s , 237 ( 1 9 8 2 )

0

0 NaI

75%

CH3CN

S y n t h e s i s , 715 (1981)

S E C T I O N 18

CARBOXYLIC A C I D S FROM ALCOHOLS

0

PhOll, PhNH

,P-c1

b

H23COOH

6

11

2

$H!O -,

90%

S y n t h e s i s , 218 ( 1 9 8 1 ) 1) COOH

(

C1S02NC0

w

2)

Hfo

* w

Et3N

wCOOH

86% S y n t h e s i s , 506 ( 1 9 8 2 )

1 ) M e l d r u m ’ s a c i d , DPIAP

0

0

II I1 Cl-C-( CH2),,-C-C1

2 ) NaBH3CN, HOAc/THF

0

0

II

II

HO-C-( CH2)n+4-C-OH

3 ) HC1, h e a t

2.50% o v e r a l l S y n t h Comm, 12, 19 ( 1 9 8 2 )

Section 18 Carboxylic Acids from Alcohols

1- 0 c t a n o l

s o l i d NaMn04 b

octanoic acid

Tetr Lett,

22,

67%

1655 (1981)

12

C O M P E N D I U M OF O R G A N I C SYNTHETIC METHODS VOL 5

CgH1 9-CH20H

C u ( Mn04 )2 CHiC1

* CgH1 gCOOH JOC,

47,

81 %

2790 (1982) COOH

CH,OH

-

1 ) blue tetrazolium s a l t 2 ) -OH

L

SECTION 18

{doH 74%

S y n t h e s i s , 739 (1980) S e c t i o n 19 Carboxylic Acids from Aldehydes

CHO

sodium c h l o r i t e NaH2P04, H20/L-Bu OH

COOH

90%

Tetrahedron, CHO

37,2091

(1981 )

COOH 77%

T e t r Lett,

23,

3131 (1982)

SECTION 19

CARBOXYLIC A C I D S FROP.1 ALDEHYDES

-

13

COOH

( b i py)H2CrOC1

-CHO

Syn Cornm,

lo, 951

( F C) C/OH O‘ OH

CHO

+

Na2C03

92%

(1980)

-coo91 %

Tetr Lett,

21, 685

(1980)

s o l i d NaMn04 octanal

octanoic acid Tetr Lett,

22,

77% 1655 ( 1 9 8 1 )

0

It

(MeO)*PH, NaOMe Ph-CHO

89%

C1 CH2COOH, MeOH

COOH

JOC,

5 , 2514

(1981)

R e l a t e d methods:

C a r b o x y l i c A c i d s f r o m Ketones ( S e c t i o n 2 7 ) .

Also via:

-

Esters

Section 109).

14

SECTION 21

C O M P E N D I U M OF O R G A N I C SYNTHETIC METHODS VOL 5

S e c t i o n 20 Carboxyl i c Acids from A1 kyl s no a d d i t i o n a l examples S e c t i o n 21 Carboxylic Acids from b i d e s

H2°

90%

acidic resin

H

H JOC,

Ph M

C

-

N

H

II

HOSO20N0

2

9, 5351

(1981)

P h -COOH

+

H2°

0

98%

Org Prep Proc I n t ,

Tetrahedron, J N s L i

36,

(1982)

1311 (1980)

0

n-BuLi -

14,357

B

'

-

d

H

85% (R)

1

CH3 Tetrahedron L e t t ,

21, 4233

(1980)

SECTION 23

CARBOXYLIC ACIDS FROM ESTERS 1) BuLi 2) Me1 3) H30t

b

“’r

15

56%

Bu

Synth Comm,

lo, 837

(1980)

Section 22 Carboxylic Acids from Amines Ph-N:

COY Pd(OAc)2

f!F4

NaOAc, CH3CN

* Ph-COOH JOC,

85%

45, 2365

Section 23 Carboxylic Acids from Esters

(1980)

0

89%

91%

Synth Comm, lJ,

0

II

~

c

\

o

c

HBr

8

H7

IPTC*

413 19

COOH

t

*hexadecyltributylphosphonium bromide JOC,

47,

154 (1982)

94%

16

C O M P E N D I U M OF O R G A N I C SYNTHETIC METHODS V O L 5

S y n t h Comm,

Q

OQ

S E C T I O N 23

12, 855

(1982)

c - 0CMe

c

1 ) CF3S020TMS

98%

2 ) H20 ONe

OMe

S y n t h e s i s , 545 ( 1 9 8 0 )

PhSeH, NaH SePh

TH F/ HrlPA

96%

JOC, 46, 2605 (1981)

O t h e r r e a c t i o n s u s e f u l f o r t h e h y d r o l y s i s o f e s t e r s may be f o u n d i n S e c t i o n 30A ( P r o t e c t i o n o f C a r b o x y l i c A c i d s ) . S e c t i o n 24 C a r b o x y l i c A c i d s f r o m E t h e r s

No a d d i t i o n a l examples

S E C T I O N 25

CARBOXYLIC A C I D S FROM ALKYL HALIDES

17

S e c t i o n 25 C a r b o x y l i c A c i d s f r o m A l k y l H a l i d e s

& C O P

hu, C O Y NaOH Co2( CO)8, P.T.C. Tetr Lett,

-

1 ) i--PrHgBr,

CuCl

2) H20,

22,

96%

1013 (1981)

COOH w i-Pr

B u l l Chem SOC Japan,

55, 3555

78%

(1982)

Chem L e t t , 571 (1980)

t

2)

H3d9

*

Bu-CH2CH2COOH

Bu2CuMgB r Tetr Lett, Tetr Lett,

21, 935 (1980) 21, 2181 (1980)

92%

18

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 25

94% Chem L e t t , 651 ( 1 9 8 0 )

1 ) BuLi

yH2Ph

2 ) g-C8H,7Br

'PH3

3 ) NaOH, H20

N

n-C8H, 7COOH

4 ) H30t Tetr Lett,

Also via:

Esters

-

22,

261 (1981)

S e c t i o n 115

S e c t i o n 26 C a r b o x y l i c A c i d s f r o m H y d r i d e s

0

S y n t h e s i s , 74 (1981)

66%

SECTION 29

19

C A R B O X Y L I C ACIDS FROM OLEFINS

S e c t i o n 27 Carboxylic Acids from Ketones

Mo(acac)2

OTMS

86'2

t-BuOOH

Tetr Lett, Bu4N@104

0 II Ph-C-CH,Br L

2, 2595

(1981)

o * Ph-COOH

dioxane

7 5%

S y n t h e s i s , 563 (1980)

Also v i a :

Esters

-

Section 117.

S e c t i o n 28 Carboxylic Acids from N i t r i l e s

CH3 (CH,),Ct\r

1 ) L-BuOK, O 2 THF, 18-crown-6 2 ) Ht

* CH3 ( C H 2 ) 5COOH

89%

JOC, 45, 3630 (1980) S e c t i o n 29 Carboxylic Acids from O l e f i n s

Ph

H2S04

CH3 +Ph-!,H-COOH

Chem L e t t , 651 (1980)

94%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

20

SECTION 30

Section 30 Carboxylic Acids from Miscellaneous Compounds Use of polymer-bound oxazolines for the synthesis o f chiral carboxylic acids:

Ph

1 ) BuLi

COOEt

I

2) BzCl

Bzrirt~C

4H '

3) H2S04 EtOH/THF

JOC,

H3C

9, 3097

45% 56% ee

(1981)

Section 30A Protection of Carboxylic Acids

0 II R-C-C1

R

= alkyl,

0 ( C H C! H$Bu

)' L i

8

* R-C-OCH2SCH3

subst. Ph, -CH20Ph Tetr Lett,

FI

R-C-OBZ

10% Pd/C

3,4539

29-72%

(1982)

R-COOH

>go%

Synthesis, 929 (1980)

H / K [Co(CN) ] removes benzyl ester protecting groups from amino asids and pe3tides in 83-94% yields.

Z. Chem, 188 (1981)

PROTECTION OF CARBOXYLIC ACIDS

SECTION 30A

0 R-C-0-CH2

21

Na2S204 +R-COOH H 20/Me CN

Synth Comm,

85-95%

12, 219

(1982)

v Br-CH2 eMOOC@-

0 I1 R-C-ONa

-

n

R-I-OCH,

-(ot COOMe

JCS Chem Comm, 1083 (1980)

Angew Chem Int Ed, 2J, 780 (1982)

rs

R-C-OH

CH2=CH-CH2SiMe3

0

+

It R-C-OSiMe3

Tetr Lett,

1 ,835 (1980)

nJ

90%

COMPENDIUPI OF ORGANIC SYNTHETIC METHODS VOL 5

22

Me Si C 1

R-COOH

R

=

C1 CH2CH2C1

-

0 II R-C-OSiMe3

SECTION 30A

%70-90%

alkyl , vinyl, ally1 , acetylenic, etc. Synthesis, 626 (1980)

0

(Me3Si)20

II

R-C-OH

H2S04

0 It e R-C-OSiMe3

'~70-90%

Chem Lett, 1475 (1980)

Ph

8

R-C-OH

It

0

Chem Lett, 1551 (1981)

SECTION 30A

PROTECTION OF CARBOXYLIC ACIDS

23

The 5,6-dihydrophenanthridine protecting group may be activated and removed by oxidation: Ce+4, H20

cef4, C ~ O R'NH2

+

+

R-COOH

0 II R-C-NHR '

Chem Lett, 991 (1982)

NaHS Used as a C-terminal protecting group in peptide synthesis. JACS,

104,3910

(1982)

Review: "Recent developments in Methods for the Esterification and Protection of the Carboxyl Group" Tetrahedron, 3, 2409 (1 980) 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).

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 3 PREPARATION OF ALCOHOLS AND PHENOLS Section 31 Alcohols from Acetylenes

Ph-CEC-CH3

1) 2 BuLi 2) BH3*THF 3) NaOH, H202

+ phn 70%

OH

OH

Tetrahedron, 36, 299 (1980) Section 32 Alcohols from Carboxylic Acids

n-C8H1 7COOH

Na BH4 TiC14

n-C 8H1 7CH 2OH

w -

93%

Synthesis, 695 (1980)

C5HllCOONa

1 ) 2 BH3.THF 2) H3@

* C5H11 CH20H

100%

Tetr Lett, 23, 2475 (1982) S

JCS Perkin I, 2470 (1980)

98%

SECTION 34A

REDUCTIONS OF ALDEHYDES TO ALCOHOLS

25

Section 33 Phenols f r o m Phenols

d°K

OH

ZnCl

t

c1

63 X

xyl ene Synthesis, 310 (1981)

Section 34 Alcohols from Aldehydes The following reaction types are included in this section:

A.

Reductions o f aldehydes to alcohols.

B. Nucleophilic additions to aldehydes, forming alcohols. C. Coupling of aldehydes to give diols. Section 34A: Reductions o f Aldehydes to Alcohols

wCHo

Na2S204 H20/dioxane/DMF JOC,

+

-

CH20H 63%

45, 4126 (1980)

26

COMPENDIUM OF O R G A N I C SYLTHETIC METHODS VOL 5

L i A l H(OCEt3)3

S E C T I O N 34A

CH20H

WCH0 *-

100% JOC,

C HO

46,

4628 (1981)

Et20

Tetr Lett, 21 , 693 and 697 (1980)

p o l y (2-v in y l p y r i d i n e ) -BH3 b

THF

-CH20H 87% JOC,

C8H1 7-CH0

1 ) Et$%,, 2 ) H202, O' H

CH

ci

-2

45,

2724 (1980)

C8H17CH20H

Tetr Lett,

a,3963

75%

(1980)

SECTION 34A

CgH1 gCHO

27

REDUCTIONS OF ALDEHYDES TO ALCOHOLS

(TFA) 2BH*THF

-

CgH19CH20H

JOC,

46,

96%

355 (1981)

CH20H

NaBH4

21

100%

ErCl

Reduces c o n j u g a t e d a l d e h y d e s i n t h e p r e s e n c e o f n o n - c o n j u g a t e d ones. Tetr Lett,

2 , 4077

( 1 981 )

Aldehydes may be r e d u c e d i n t h e p r e s e n c e o f k e t o n e s :

ao t

o n l y 4% Chem L e t t , 461 (1981)

28

COMPENDIUM OF ORGANIC S Y K T H E T I C NETHODS VOL 5

S E C T I O N 34A

0 21 4 (1 981 )

Synthesi s

0 It

HC-ONa

O P

b

Me

CH20H

JOC,

9, 3367

69%

(1981)

1 ) [HCOOH

f

ZEtMgBr]

w

2 ) $0

CH20H

~ 7 0 %

Tetr Lett,

22,

621 (1981)

S E C T I O N 348

NUCLEOPHILIC A D D I T I O N S TO ALDEHYDES,

29

FORMING ALCOHOLS

( EtO) ilSi HMe

WCH0 KF

w

Ph

M Ph

H

2

0

H

95%

JCS Chem Comm, 121 (1981)

(Ph3P )2CuBH4 Ph

WCH0

4

Ph

w

Tetr Lett,

Ph-CHO

A12Te3, H20

+

22,

CH20H 99%

675 (1981)

Ph-CH20H

Angew Chem I n t Ed,

100%

19,1008

and

1009 (1980)

34B:

N u c l e o p h i l i c A d d i t i o n s t o A l d e h y d e s , Forming A l c o h o l s

Aldol reactions are l i s t e d i n : S e c t i o n 324 ( A l d e h y d e - A l c o h o l ) and S e c t i o n 330 ( K e t o n e - A l c o h o l )

30

COMPENDIUM

OF O R G A N I C SYNTHETIC METHODS VOL 5 SECTION 34B OH

Angew Chem I n t Ed,

19, 1011

(1980)

Et

OCH0 1 ) TiC14

2 ) Et2Zn

S y n t h Comm,

C6H, 3CH0 t

-

--------tC

11,261

(1981)

H 1 H C-OH 6 131 Pr

73%

Pr-CrC1 (THF)3 Ketones a r e r e l a t i v e l y u n r e a c t i v e . Angew Chem I n t Ed,

21, 144

(1982)

SECTION 34B

NUCLEOPHILIC ADDITIONS TO ALDEHYDES,

31

FORMING ALCOHOLS

Ph

Ts

Tetr Lett,

23,

1609 (1982)

1 ) BuLi 2 ) C8H17CH0 3 ) NaBH4, PdL4

* Ph

OH 73%

Chem L e t t , 1331 (1982)

>-

- - YHoH SiMe3

CHO

T i C l 4 , CH2C1? - -

I,

Organometallics,

8 0%

1,1651

(1982)

32

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

m

T i (NEt2)3

0-C- N (LPr ) II 0

OCb

Angew Chem Int Ed,

SiMe

-

CH3CH0

TiC14, CH2C12

JACS,

MgCl t

Cp2ZrC1

SECTION 348

CHO

21, 372

(1982)

OH -

-Ph v -c

m3

104,4963

76% 86% ee

(1982)

-+ OH

90%

88% threo

Tetr Lett, 22, 2895 (1981)

SECTION 348

33

N U C L E O P H I L I C ADDITIONS TO ALDEHYDES, FORMING ALCOHOLS

Tetr L e t t ,

Ph-CHO

CrC13, LiA1H4

t

Br

w

Ph

t

-

_c"3 96%

100% threo

or CrCl

Tetr L e t t ,

w1

23, 3497 (1982)

2, 1037 (1981)

OH

1 ) Sn, THF 2 ) H20

Ph

-CHO

Ph Chem L e t t , 1527 (1981)

34

COMPENDIUM

OF O R G A N I C SYNTHETIC METHODS VOL 5

Me0

PhCHO

4H

Ph

A1 E t 2

SECTION 348

"H

83%

Me0

vi2

JCS Chem Comm, 845 (1982)

PhCHO

Me\

-

Ph

73%

Me

N-NMe2

1

T i (O-i-Pr)3 Angew Chem I n t Ed,

21,

864 (1982)

Me2CuLi $CHO OCH 2O Bz

BzOCH20

OH

>20:1 d i a s t e r e o s e l e c t i v i t y Tetr Lett,

21,

1031 and 1035 (1980)

CH3CH2CN t

Bu2BOTf i -Pr2NEt

*

;H3 Ph-CH-CH-CN bH

Ph-CHO Chem L e t t , 1401 (1982)

90%

S E C T I O N 348

N U C L E O P H I L I C A D D I T I O N S TO ALDEHYDES,

35

FORMING ALCOHOLS

-

OMe t

THF O

C

u

H

OMe

90% OH

O JACS,

102, 6900

(1980)

PhCHO

+

1 ) Zn, THF

2) H k , - O 0T H P

p

*

Ph-CH-CMe2COOH

I

88%

OH

Bull SOC C h i m F r a n c e 11, 145 (1980)

L iCfC-TMS

C h e m L e t t , 255 (1980)

36

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

‘0 O ‘ Ac

C-HO

S E C T I O N 34B

____t

TiC14

OH 60% Tetr Lett,

34C:

22,

3269 (1981)

C o u p l i n g o f A l d e h y d e s t o G i v e Diols

2 Ph-CHO

1 ) Fe(C0)5, p y r i d i n e

e

88%

Ph-CH-CH-Ph

dH 6 H

2 ) H30Q

Chem L e t t , 1141 (1980)

2 Ph-CHO

TiC13 NaOH

OH

I

OH

1

Ph-F-F-Ph

k i i Tetr Lett,

R e l a t e d methods:

3 , 3517

A l c o h o l s f r o m Ketones ( S e c t i o n 4 2 )

(1982)

SECTION 37

37

ALCOHOLS FROM AMINES

S e c t i o n 35 Alcohols and Phenols from A 1 k y l s , Methylenes and Aryls No examples of t h e r e a c t i o n R R ' ROH ( R ' = a l k y l , a r y l , e t c . ) ROH occur i n t h e l i t e r a t u r e . For r e a c t i o n s o f t h e t y p e RH ( R = a1 kyl o r a r y l ) s e e S e c t i o n 41 (Alcohols a n d Phenols from Hydrides). -+

-+

S e c t i o n 36 Alcohols from Amides

LiEt3BH NP Ie

-+

CH20ti

JOC,

45,

1 (1980)

0ti

1 ) Phl-IgBr N

95%

+

2 ) ClePlgCl 3 ) H30+

N 'CH3

I

Ph-

I I

C-

Me

82%

H

Tetr Lett,

2,1085

(1981)

S e c t i o n 37 Alcohols from Amines Ph

')

n-C

-

H NH 16 33 2

Ph

Ph BF4

0 "C16H330H II

%50%

P.T.C.

J . C . S . Perkin I , 1492 (1981)

38

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 38

Section 38 Alcohols from Esters 0 II C5H1 ,C-ONe

NaBH4 polyethylene glycol

,

0 11 CH3 ( CH2 ) 6-C -0Me

80%

* C5H, CH20H JOC, NaBH4

t-BuOH, MeOH

46, 4584 (1981)

CH3 (CH2) 6-CH20H

Synth Comm,

It C-NMe2

NaBH4 EtOH

-SEt

CH20H Synth Comm,

LiBH4 +E-OEt

(1982)

0

0 - NPle

s

12, 463

79%

( Me0 ) B

11,599

93%

(1981)

81%

=

JOC, 47, 1604 (1982)

SECTION 38

ALCOHOLS FROM ESTERS

COOEt

39

CH20H

BH3*SMe2

89% THF, r e f l u x S y n t h e s i s , 439 (1981 1

JOC, 47, 3153 (1982)

94%

JOC,

45,

1 (1980)

1 ) HSi(OEt)3 CsF H2C=CH (CH2)8-COOMe

2) $0

* H2C=CH ( CH2)8CH20H 70%

S y n t h e s i s , 558 ( 1 9 8 1 )

40

SECTION 3 8

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

34% Tetr Lett,

EtCOOCH3 Cp2TiC1

t

21, 2171

and 2175 ( 1 9 8 0 )

OH I * Et-C-Pr

83%

1

H

PrMgBr

Tetr Lett,

21, 2171

a n d 2175 ( 1 9 8 0 )

7 2% JOC,

45,

1828 (1980)

1 ) NaH, 1-BuX

0

II NsC-CH2-C-SBz

2 ) NaH, PhCH2X

i-Bu

-1

P4 z C - C - C H *OH

I

3 ) NaBH4

CH2Ph

Tetr Lett,

2, 3151

(1982)

76%

ALCOHOLS AND PHENOLS FROM ETHERS AND E P O X I D E S

S E C T I O N 39

R e l a t e d Methods:

41

C a r b o x y l i c A c i d s f r o m E s t e r s - S e c t i o n 23, P r o t e c t i o n of A l c o h o l s - S e c t i o n 45A H y d r o l y s i s o f E s t e r s i s c o v e r e d i n S e c t i o n 23

S e c t i o n 39 A l c o h o l s and P h e n o l s f r o m E t h e r s and E p o x i d e s

BBr3, NaI 100%

CH2C12, 15-crown-5

Me0

HO

Tetr Lett,

OMe

22,

4239 (1981 )

B B r 3 * SMe2

%80% R

R

Tetr Lett,

1, 3731

(1980)

0 OH

OEt MeSiC13 Na I

w

Angew I n t Ed,

20,

690 (1981)

85%

42

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

S E C T I O N 39

OH

OMe

i

1 ) Me3Si I , p y r i d i n e 89%

2 ) CH30H

Org Syn,

3,35

(1980)

MeSSiMe3

R-OH

o r PhSSiMe3

Tetr Lett,

% ,

21, 2305

90%

(1980)

S y n t h e s i s , 396 ( 1 9 8 1 )

SiC14 Ph-OMe

Na I

*

Ph-OH

S y n t h e s i s , 1048 ( 1 9 8 2 )

90%

S E C T I O N 39

ALCOHOLS AND PHENOLS FROM ETHERS AND E P O X I D E S

43

OH

OMe 1 ) PhMeNNa, HMPT

%80-90%

R

Syn t hes i s , 638 ( 1 980)

L i A l H4 +

benzene OMe

OMe

OH

OEle 67%

JCS Chem

Comm, 507 (1980)

OMe

COOH

COOlle

JOC,

46,

1991 (1981)

44

COMPENDIUbl OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 39

Additional examples of e t h e r c l e a v a g e s may be found i n S e c t i o n 45A ( P r o t e c t i o n o f Alcohols and P h e n o l s ) .

Nafion-H 73%

H20/THF

0/”\

I-I-CH20H

S y n t h e s i s , 280 (1981)

OH

Red-A1

CH-CH2-CH20H 95%

Tetr Lett,

3,4541

(1982)

Bzo OH

Tetr L e t t ,

3,2719

(1982)

SECTION 39

sugar

ALCOHOLS A N D PHENOLS ;FRObl ETHERS A N D E P O X I D E S

bo

45

{TOH

BH3.THF, NaBH4 4

Can be accomplished i n the presence o f OTs, k e t a l , a n d a c e t a l groups. JOC,

5,3836

2Me3A1

A

Me

Me

*

BuLi

(1980)

OBz

K

B

Me Angew Chem I n t Ed,

Bu-Li

+

z 7 6%

1, 71

/

Et3N +

Bu

(1982)

7 9%

J=LOH 1.

Tetr Lett,

94%

22,

577 (1981 )

46

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

S E C T I O N 39

* PdL4

‘gH1 7

&

C H ( C02P4e)

‘gH1 7 Tetr Lett,

T I 0 0 3 )3 hexane

84%

11,2575

(1981)

Tetr Lett,

76%

1, 1149

(1980)

1 ) LDA

2,

4

3 ) NH,C1

Synth

Comm, lJ,

49 ( 1 9 8 0 )

SECTION 39

ALCOHOLS AND PHENOLS FROM ETHERS AND EPOXIDES

47

Tetr Lett, 21, 4365 (1980)

Hx-CECH

1) Me3A1 , Cp2ZrC12 2) BuLi

Hx 87%

Me

Synthesis, 1034 (1980)

JOC,

45,

2579 (1980)

48

COMPENDIUM

OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 40

S e c t i o n 40 A l c o h o l s from H a l i d e s

n-C8H, 7C1

.p o l -ymer-bound

carbonate

benzene

n-C8H1 70H

t

90%

S y n t h e s i s , 793 (1981)

0

JOC,

47,

4024 (1982)

0

n

K2C03/acetone o r Bu4NOH/DEIF

85-90% Steroids,

Bu B r

P h L i , CO

3, 345

(1982)

Ph2C-OH

80%

I

Bu

JOC,

46,

4625 (1981)

SECTION 41

ALCOHOLS AND PHENOLS FROM H Y D R I D E S

Tetr Lett,

2, 1085

49

(1981)

1) E - B u L i

64%

2 ) CH3CH0

Br

HO-CHCH3 JOC,

45,

1514 (1980)

S e c t i o n 41 A l c o h o l s and P h e n o l s f r o m H y d r i d e s

t-BuOOH,

Se02

+

1 y C H 2 0 H 100%

s i l i c a gel

Chem L e t t , 1703 ( 1 9 8 1 )

50

COMPENDIUM OF ORGANIC SYNTAETIC METHODS VOL 5

,go

KHS05'KHS04' K2S04

-H

NaHC03, H20/THF

-R

Tetr Lett,

6

')

0,

SECTION 41

11,4201

(1981)

-

H3P04

2 ) H202, HC1, MeCN

%75% OH

Tetr Lett,

22,

2337 ( 1 9 8 1 )

OH H2°2

Me

SbF5/HF

88%

HO

Me JCS Chem

Comm, 1128 ( 1 9 8 0 )

S E C T I O N 41

ALCOHOLS AND PHEN3LS FRON H Y D R I D E S

51

?IH2 tNH2 HOOC,

OH

,c=c HO

P H

OH

'COOH

70%

02, p e r o x i d a s e

*

COOH

COOH

JACS,

103,6263

(1981)

1 ) '02

66%

2 ) NaBH3CN

Tetr Lett,

a

Ph-C-CH3

PhI=O or P ~ I ( O A C ) ~

-

OH, CH30H

w

3,1717

(1982)

0 II Ph-C-CH20H

Tetr Lett,

2, 1283

60%

(1981)

52

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 41

1 ) Me3Si I , HMDS

0

J Y

2 ) Os04, NMMO 3 ) H20

Ph

98%

Ph

OH

T e t r L e t t , 22, 607 (1981)

&

-

OSiMe3

b

Cr02C1

7 6%

Tetr Lett,

P h - C H C OOMe

1) P ~ I ( O A C ) ~ 2 ) KOH, li20

*

&CH3

23,

2917 (1982)

s:

50%

Ph- H-COOH OH

3 ) Ht

Tetr Lett,

2, 2747

(1981)

S e c t i o n 42 A l c o h o l s f r o m Ketones The f o l l o w i n g r e a c t i o n t y p e s a r e i n c l u d e d i n t h i s s e c t i o n :

A.

Reductions o f ketones t o alcohols.

B.

N u c l e o p h i l i c a d d i t i o n s t o ketones, f o r m i n g a l c o h o l s

C.

Coupling o f ketones t o g i v e d i o l s .

SECTION 42A

REDUCTIONS OF KETONES TO ALCOHOLS

53

42A: Reductions o f Ketones to Alcohols

(CH2)6C00H

CHO

-4

( CH2) &OOH

NaBH4 ErCl

75%

CHO

Tetr Lett, 22, 4077 (1981)

NaBH4 0

Fon ta ine bl eau sand

b

JCS Chem Cornrn, 1066 (1981)

H2/NaH

85%

RONa, Ni (OAc)* JOC,

45, 1946

(1980)

54

COMPENDIUM OF O R G A N I C SYNTliETIC METHODS VOL 5

S E C T I O N 42A

98%

S y n t h e s i s , 214 (1981)

0 OH

p o l y ( 2 - v in y l p y r id i n e ) -BH3 THF JOC,

45,

94%

2724 ( 1 980)

(TFA)2BH*THF 7 6%

JOC,

46,

355 (1981)

OH

-0

NaBH4-CeC1

JACS,

103,5454

(1981)

97%

REDUCTION OF KETONES TO ALCOHOLS

SECTION 42A

b

55

t-BuNH2*BH3

87%

Et20 Tetr Lett,

1, 693

and 697 (1980) OH

0

LiBuBH3, -78' to1 uene/hexane

96%

JOC,

CH3-!-

0

0 (CH2)3-d-OMe I

-

LiA1H4-Si02 ether

47,

3311 (1982)

0 1 CH3-bH(CH2)3-d-OMe OH

Tetr Lett, 23, 4585 (1982) OH

JOC,

47,4640

(1982)

84%

COFIPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

56

SECTION 42A

OH

0

Na2S204

97%

H20/dioxane/DMF

6 0

JOC,

5, 4126

(1980)

OH HCOOH

78%

RuCl 2L3 Bull Chem

SOC

Jpn,

55,

2441 (1982)

JOC, 46, 3367 (1981)

H2Se , hv

Angew Chem I n t Ed,

53%

19, 1008 a n d

1009 (1580)

SECTION 42A

&

REDUCTION OF KETONES TO ALCOHOLS

57

1 ) Ph2SiH2 L3RhC1

97%

2) CH30H Organometallics,

0 ii

Ph-C-$H-CH3

Br

3

(Et0)2Si HMe

KF

+

1,1390

(1982)

PH

Ph-bH-CH-CH3 I Br

7 0%

JCS Chem Comm, 121 (1981)

1 ) (Ph3P)3RuC12 Et3SiH 2) H30t, MeOH

-

H I

N

O

H 95% equatorial

JOC,

NaBH4, Ce MeOH

3+

-

47,

2469 (1982)

-OH 0

Synth Comm,

0

lo, 623

85% 98% trans

(1980)

58

COMPENDIUM OF O R G A N I C SYNTAETIC METHODS VOL 5

IlaBH4 H3C

H3C&OH

mandelic a c i d

c

86%

H

3,212

I n d J . Chem,

i,

S E C T I O N 42A

(1982)

H

( Ph3P)2CuBH4

91 %

H Tetr Lett,

2, 675

(1981)

LiBH3CH3 92% -7B0,

ether

CH3

S y n t h Cornm,

12, 723

(1982)

SECTION 42A

REDUCTIONS OF KETONES TO ALCOHOLS

59

83% 99% e r y t h r o Tetr Lett,

22,

4723 (1981)

+

COOMe

OH

85% >99% e r y t h r o

60

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

{fi

SECTION 42A

(Jj

NaBH4-PdC1 THF/H20

96%

Chem L e t t , 1029 ( 1 9 8 1 )

JOC,

P r o s t a g 1and i n

45,

1 (1980)

i - B u 2 A l -0

c

F c

OH

95% 92% s t e r e o selectivity

B u l l Chem SOC Jpn,

3,3033

(1981)

SECTION 42A

REDUCTIONS OF KETONES TO ALCOHOLS

61

Na2S204

*

DMF/H20

&OH

75% y i e l d 85% endo

c

Tetr Lett,

22, 179

(1981)

HO MeTi (OL-Pr)3

87% QH3

H e l v Chim A c t a ,

63,

2451 (1980)

OH

86%

82% cis

JOC, 45, 1041 (1980)

62

COMPENDIUM OF ORGANIC SYNTiiETIC METHODS V O L 5

1 ) t-BuNH2 (protects the aldehyde) 2) L i (t-Bu0)3Al H 0

-

H

3)

Hp

SECTION 42A

*

4) basic alumina CHO

H Tetrahedron, 38, 1827 (1982) Potassium tri (R,S-s-butyl )borohydride reduces 3-OX0 steroids to the axial alcohols, without affecting the 17- and 20-ketone groups. Use of a chiral hydrosilane-rhodium phosphine reagent allows greater stereoselectivity of 17a-alcohol formation than with other methods.

JCS Chem Comm, 1238 and 1239 (1982)

SECTION 42A

0 II Ph-C-Et

REDUCTION

OF

KETONES TO ALCOHOLS

NaBH4

63

Hy O H Ph’*‘Et

w

chi ral gl ucose derivatives

100% 51% ee

JOC, 45, 4229 (1980) JOC, 45, 4231 (1980) Bull Chem SOC Jpn, 54, 1424 (1981)

2-octanone

-

(S)-2-octanol 79% ee

similar conditions

HO w

+ , /

C5H1 1/

H

/ C

‘C-C-CH 3

79% 91% ee

JOC, 47, 2496 (1982) JOC, 47, 2814 (1982)

64

COMPENDIUM OF O R G A N I C SYNTHETIC NETHODS VOL 5

SECTION 42A

2 ) H202, NaOH

JOC,

89% ee

47,1606

(1982)

-

OH

452

55% e e

45, 582 (1930) JOC, -

L i A 1 1i4

N-methyl ephedri ne

-

ti

H

OH

92%

78% ee JCS Chem Comm, 1026 (1980) Chem L e t t , 981 (1980)

SECTION 42A

REDUCTION OF KETONES TO ALCOHOLS

LiAlH

Et-C-C=CH

U0

+

ephedrine

65

7

60-80%

Et-C-CrCH I

84% ee

OH

Tetr Lett, 21, 1735 and 1739 (1980)

r

0 It

P

\E t Et 93% 68% ee Tetr Lett,

g,4111

B'\

(1982)

85% 90% ee

c*c

H T e t r L e t t , 22, 247 (1981)

-

66

COMPENDIUM OF O R G A N I C SYNTFiETIC METHODS V O L 5

"[

L i binaphthyl

0 I1

R-C-R'

0'

S E C T I O N 426

A,l

R'

P, = a l k y l

R ' = v i n y l , Ph, a c e t y l e n i c

Pure and Appl Chern,

53, 2315 (1931)

2H2, NaBr RaNi, t a r t a r i c a c i d 65% ( R , R )

-54O

[a] =

B u l l Chem SOC Japan,

0 I1

CH3( Cli2)6C-CH,COOMe L

c h i r a l N i complex

CH3(

53,

3367 (1980)

OH

CH2)6-H-Cti,C00f4e

Rill1 Chern SOC Japan,

_55,2186

(1932)

SECTION 42A

0

Ph-ld-COOEt

TO ALCOHOLS

REDUCTION OF KET3NES

c t i ir a 1 d ih y d r o p y r id in e

Mg++

67

OH

*

Ph-iH-COOEt

30%

83% ee

103, 2091

JACS,

(1931)

JACS, 103, 4613 (1931) L -

0 II

Ph-C-CH2C1

ArPhSi HZ RhCl D i o p

HIC\\\OH

* PTI’

63% ee

‘CH2C1

J Chem R e s e a r c h j S ) , 320 (1920)

0 II

P 11- C- CH2C 1

microbial reductio4 n

Hu, @H Ph’

JOC,

C

g,3352

cti2c1

(1920)

80% 100% ee

68

OF ORGANIC SYNTHETIC METHODS V O L 5

t:w COMPENDIUM

SECTION 428

microbial reduction

JOC,

47,

60%

2320 (1982)

Use of LiAlHq-aminodiol complexes to reduce ketones asymmetrically. The chiral aminodiols are synthesized from tartaric acid. H

H Chem Ber, 113, 1691 (1980)

42B:

Nucleophil ic Additions to Ketones, Forming Alcohols

Aldol reactions are 1 isted in Section 330 (Ketone-Alcohol ) .

SECTION 428 NUCLEOPHILIC ADDITIONS TO KETONES, FORMING ALCOHOLS

(85%

JOC,

a)

5,536%

(1992)

Chem Lett, 1679 (1931)

n-C3F71 , SnCl

___)

DMF/ pyr id ine Chem Lett, 1337 (1931)

69

70

COMPENDIUM OF ORGANIC SYNT,iETIC METHODS V O L 5

-

BCS J a p a n ,

25,561

SECTION 425

(1932)

SiMe3

64%

TiC14, CH2C12

Organornetall i cs,

T e t r Lett,

22,

1,1651

( 1932)

4985 (1931)

SFCTION 42B

NUCLEOPHILIC ADDITIONS TO KETONES, FORMING

71

ALCOHOLS

w1 (DMI

=

1,3-dimetiiyl-2-imidazol i d i n o n e ) Chem L e t t , 1507 (1930)

Bu,B

L

Bu

+

Chern L e t t , 993 (19DO)

72

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

S E C T I O N 423

JOC, -47, - 2325 ( 1 9 2 2 )

1) t-BuLi

3 ) ti20

Tetrahedron,

33,

3997 (1931)

1) H2C=C=CHTMS, T i C 1 4

sC-H

2 ) KF, Me,SO

89’4

L

JCC, 45,

3925 ( 1 9 8 0 )

SECTION

42B

N U C L E O P H I L I C A D D I T I O N S TO KETONES, FORMING

73

ALCOHOLS

Do

0 Ph I,

OH

I

1) ( E t O ) P - -0TMS 2 &

2 ) He

83% Tetr Lett,

NC

y:”

(EE = ethoxyethyl)

-

21,1017

J O C , 45, 395 (1980)

(1980)

COMPENDIUM OF ORGANIC SYNT,iETIC METHODS VOL 5

74

1) t--BuMgBr

SECTION 428

OH I

f

MetiiiC

95% ee T e t r a h e d r o n , 36, 227 (19133)

N

II

x

1) t-BuLi

H - C- NMe2

2)

0

0

*

3 ) MeOti, tI2O 4 ) KOH, HO,

JACS,

H8 NHMe

m, 7125 (1980)

Li

I

H JCC,

45%

5,447

(1980)

57%

S E C T I O N 44

ALCOHOLS FROM OLEFINS

75

C o u p l i n g of Ketones t o G i v e D i o l s

42C:

HO Ce-

OH

I

95%

2

Tetr Lett,

R e l a t e d methods:

g,1353

(1982)

A l c o h o l s f r o m Aldehydes ( S e c t i o n 34)

S e c t i o n 43 A l c o h o l s and Phenols from N i t r i l e s

No A d d i t i o n a l Examples,

S e c t i o n 44 A l c o h o l s f r o m O l e f i n s F o r t h e p r e p a r a t i o n o f d i o l s f r o m o l e f i n s see S e c t i o n 323 (Alcohol-Alcohol)

NaBH4, TiC14

71%

DME

JCS Chem Comm, 414 (19CO)

76

COMPENDIUM OF O R G A N I C SYNT;IETIC METHODS VOL 5

SECTION 44

1 ) isopi nocampheyl borane 2 ) NaOH, H202

73%

JOC,

v

96,

2933 (1981)

OH

1) d i 1o n g i f o l y l borane

I

b

2 ) H202, NaOH

fi 1% 71% e e J3C, -4 6 , 2988 (1981)

1) H g ( O i i ~ ) H20, ~, P.T.C 9 7%

2 ) NaBH4

OH

JACS,

102, 7793

(1930)

S E C T I O N 44

ALCOHOLS FROM OLEFINS

77

OH

CH3 87%

JACS, 102, 7335 ( 1 9 8 0 ) ~

PhSO -CH-Bu 2 1 Li

Bu3B B u l l Soc Chim F r a n c e 11, 99 (1981)

1) ( PhS)3C-Li 2 ) Hg

I 1 or Me02SF

JCS Chem Comm, 1149 ( 1 9 8 1 )

78

SECTION 44

COMPENDIUM OF ORGANIC SYNTJETIC METHODS VOL 5

CH3( CH2)9CH=CH2

BH~CIP * CH3( CH2)9CH2CH20H

83%

B F3*0Et2

JX,

46,

( PliSe)2 , MgS04

MeCN/H20

5214 (19G1)

P

OH

AcO

electrolysis JACS, 103, 4606 (1981) Section 45 Alcohols from MisLellaneous Compounds No Additional Examples

For conversions o f boranes to alcohols, see Section 44

89%

SECTION 45A

PROTECTION OF ALCCHOLS AND PHENOLS

79

Section 45A _Protection o f Alcohols and Phenols

R-0-THP

R-OH

MeOH , ( Me3Si 0)*SO2

Synthesis, 899 (1931)

R-OH

polyvinyl pyridinium tosylate

* R-OTHP %GO-90%

? =

0

1 ,

2O,

'3 alkyl , benzyl , etc. JOC,

46,

5044 (1981)

80

COMPENDIUM OF ORGANIC S Y N T # i E T I C METHODS VOL 5

SECTION 4 5 A

C 1 C 0 0 C H CH TMS

pyri d i n e

0

L-1

R- 0- C - 0 C l i CH2TMS

R-OH

Bu4NF, THF

or Z n B r 2 ,

Cti3N02

Tetr Lett, 22, 969 (1981) U

2 ) NH40H

22, _ 1933 (1931) Tetr Lett, _

S E C T I O N 45A

PROTECTION

OF A L C O H O L S AND P H E N O L S

81

L

N a I , HMPA Ar-OH

Ar-OCH2SPh

S y n t h Comm,

R-OH

20,9 1 1

(1980)

CH, ( OMe) Nafion-H,

5 7-96

R - 3- C t i 2 0 M e

i

00

S y n t h e s i s , 4 7 1 (19G1)

, i F c1 -c

NO2

Cleo t i / H 0 Synth Com,

20,463

(1980)

82

COP4PENDIUP4

OF O R G A N I C S Y N T d E T I C METHODS V O L 5

S E C T I O N 4511

gcoc1

dE t

R-OH OEt

T e t r Lett,

2,3719

(1931)

0 I1

OCCl

0 R-0-C-0

I?-OH

Tetr Lett,

2,3 5 9 1

(1981)

S E C T I O N 45A

PROTECTION OF ALCOHOLS AND PHENOLS

83

0 I1

PhS02CH2CH20CC1

2 0 II

R-O-COCH2CH2S02Ph

R-OH

(R-O-PSEC)

Tetr Lett,

z,3667 ( 1 9 3 1 )

GuM-C1 50% NaOH

R-OH

(GUM = g u i a c y methy

R-O-GUM

1 T e t r L e t t , 22, 1973 (19C1) L

K- 0 - C H 2 & X l e

DDQ

w

R-OH

CH,C1 2/H,0 L

L

I s o p r o p y l i d e n e , THP, MEM, TMS, Bz, e t c . groups a r e u n a f f e c t e d . T e t r L e t t , -23, 885 and 339 ( 1 9 3 2 )

84

C O M P E N D I U M OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 45A

H3C&H2CI

K2C0,, K I , CH3CN

Ar-OH

Ar-0

pH CH3

4 atm H2 Pt02

Ar = s u b s t . P h S y n t h e s i s , 987 (1982)

b a s e , BrCH2C6H4CN

R-O-CH2

R-OH

CN

el ectrol ys i s

Chem Ber,

114,946

(1981)

PROTECTION OF ALCOHOLS AND PHENOLS

SECTION 45A

BF3-Et20

R-0-BZ

+

Me2S

a5

R-OH

-

Chem Pharm Bull , 23, 3662 (1930)

Ph3CC1 , CH2C12

Ph3C-0

OH

ZnBr2

/ Tetr Lett, Tetr Lett,

R-OH

Me3SiCH,CH=CH2 L

+

21, 2633 21, 3243

.;iii OH

(1980) (1980)

R-0-SiMe3

I2

Chem Lett, 85 (1931)

>go%

86

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

R-OH

SECTION 45A

R-0-Si (jrPr)3

(More stable to HS than t-butyldimethylsilyl) JOC,

s,4797

(1980)

HC: C

C1SiMe3, Et3N

OSi Me3 >80%

cat. DMSO or HMPA

Rec Trav Chim Pays-Bas, 2, 70 (1930)

R-OH

R-OH

CH2=CH-CH2-Si Me3 CH3CN

-

CH2=CH-CH2SiMe2t-Bu CH3CN

R-OSiMe3

-

..go%

R-OSiMe2t-Bu

Tetr Lett,

21, 835

(1930)

S E C T I O N 45A

a7

P R O T E C T I O N OF A L C O H O L S AND P H E N O L S

C1 CH20CII,CH,TMS L

L

R- OCH ,OCH CH2TMS

R-OH

L

Tetr Lett, 21, 3343 ( l 9 E O )

R-OH

F3C-S03H,

,

CH2C1 L

H2C=CH-CH2SiMe3

*

Synthesis,

0

92-96%

R-0-SiMe3

745 (1931)

0

Me AcCII=C-O-X

85%

X = SiMe2-t-Bu

Tetr Lett,

22, 1299

and 1303 (1981)

aa

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS V O L 5

SECTION 45A

OCH cti 3 II I 3 / CF3-C-N-Si-C(CH3)3 \

C;H3 R - 0 - S i - C - C (CH3)3

R-OH

I

9 6 - 100%

CH3 JOC,

R-OSiMe2t-Bu

_4L, 3336

(1932)

NBS

DMSO

R-OH

S y n t h e s i s , 234 (1933)

R-0-Si M e g - B u

L i BF4

* I?-OH Tetr Lett, 21, 35 (1980)

R-CH-OTs I

R’

K, c r o w n e t h e r diglyme

e

R-CHOH I

R’ Chem Pharm B u l l

, 3,3 1 7 3 (1382)

SECTION 45A

89

PROTECTION OF ALCOHOLS AND PHENOLS

Use o f t h e l e v u l i n o y l g r o u p as an O t i - p r o t e c t i n g g r o u p i n t h e synt h e s i s of o l i g o s a c c h a r i d e s .

Removed b y h y d r a z i n e .

Rec T r z v Chim Pays-Gas,

jl, 6 5 (1981)

I2 sugar

0x01 ane

0-C t i =C ti! le

OH

JCS Chen Comrn, 1274 (1982)

OR Tetr Lett,

23, 2641 (19C2)

90

CObIPENDIUM OF O R G A N I C SYNTiiETIC EIETHODS V O L 5

(5-Bu ) 2S iC 1

OH

0

\

t-EU

Si

/-

't-Bu -

0'

Et3N

OH

SECTION 45A

Removed u s i n g p y r i d i n i u m h y d r o f l u o r i d e .

%

5 0 - 30 2

T e t r L e t t , 22, 4993 (1381) L-

P r o t e c t s 1,2-,

1,3-,

and 1 , 4 - d i o l s .

D e p r o t e c t e d by 4G% aqueous

HF i n CH3CN. T e t r L e t t , -23, 4871 (1982)

OH

OAc activated

Zn

Me-"

190% Tetr Lett,

22,

335> (1931)

SECTION 45A

PROTECTION

OF ALCOHOLS A N D PHENOLS

91

b KOH, Cti,6r,

OH

BzO G

L

O

P

h

L

DMSO

OPh

6zO OBZ

OBZ

43% Synthesis, 421 (1982)

CH3

Removed using SnC14, followed by

-

2.90% OH.

JOC,

46,2419

Related Methods: Ethers from Alcohols Alcohols from Ethers Esters from Alcohols Alcohols from Esters

-

Section 123 Section 39 Section 103 Sectioil 3G

(1981)

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 4

PREPARATION OF ALDEHYDES Section 46 Aldehydes from Acetylenes

Ph-CEC-Ph

-

(BiPy)H2CrOC15

96%

2 PhCHO

Org Prep Proc I n t ,

14,362

(1982)

Tetr L e t t ,

2,2921

(1981)

Tetr L e t t ,

2,1041

(1931)

S E C T I O N 47

ALDEHYDES FROB1 CARBOXYLIC A C I D S AND A C I D HALIDES

93

S e c t i o n 47 Aldehydes f r o m C a r b o x y l i c A c i d s and A c i d H a l i d e s

59%

S y n t h e s i s , 8 7 1 (1981)

0 I1

Et-C-OH

1) PPA,

a';::?

2 ) NaOEt, EtOli 3 ) Me1

L

E t -CHO

>

%45%

4 ) LiA1H4

5) H3@ S y n t h e s i s , 303 (1991) C

72% JCS P e r k i n

I , 2470 (1980)

94

S E C T I O N 47

C O M P E N D I U M OF O R G A N I C S Y N T H E T I C METHODS VOL 5

A ( C H 2 ) 8 - t -0C 1

NaBH4, p y r i d i n e

DHF,

THF,

+

6

-70' S y n t h Cornrn,

0

A ( CH2)8-C-C1 I1

I1

C H 3 ( C H 2 ) 5-C-C1

12, 839

(1982)

1) NaBIi4 2 ) EtCOOH, HC1

E t O C H =CH2

+

Tetr Lett,

0

( CH2)8-CII0

Bu,SnH 3

( CH2)3-CH0

22,

11 (1981)

3 1%

CH3(CH2)5-CH0

+

PdL4

~ 5 3 %

J C S Chern Cornrn, 432 (19DO) J O C , 46, 4439 (1981) 1

0 I1

CH3( C H 2 ) 7-C-C1

L2CuBH4 +

CH3(Cti2) 7-CH0

JGC,

G , 3449

(1980)

76%

SECTION 47

ALDEHYDES FROM CARBOXYLIC A C I D S AND A C I D HALIDES

95

+-

0 I1

P h - C-TIIS

Bu4NF

*

Ph-CHO

75%

H,O/TH F L

Tetr Lett,

22, 1881

(1931)

OH I

Ph-CH2-CH-COOH

Ph-CH2-CH0

97-101%

47, 3006 ( 1 9 8 2 ) JOC, -

OH I

Bu-CH-COOH

Bu,NO 10, Q Y

4

P

90%

Bu-CIIO

CHC13 o r d i o x a n e

S y n t h e s i s , 563 ( 1 9 8 0 ) Tetr Lett,

3,2655

(1980)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

96

1)

0 CH3( CH2) 16-C-COOH I1

fN)

TsOH

H benzene

2 ) H30B

-

SECTION 47

0 C H ~ (C H ~ 1) 6 - ~ - ~ It

100%

Tetr Lett, 23, 459 (1982) c

CH2COOH

I

CHO

6 Bu4N 1 0 4 '

70%

C1{Cl3 or dioxane bMe

OMe

Synthesis, 563 (1920) T'etr Lett, 21,2655 (1980) Section 48 Aldehydes from Alcohols

@*Cr03 eHC1 (on

Alumina) 87X

Synthesis , 223 (1930)

SECTION 48

ALDEHYDES FROM ALCOHOLS

CTHP

97

(Phen) CrOCl

35%

CH20H

-

CH20H

Tetr Lett,

b

Cti2C12

21, 1583 (1980)

-CHO 82%

Synthesis, 69 1 (1980)

-CH20ti

poly( vinyl pyridinium) dichromate cycl ohexane

JOC, -46, 1728 (1981)

b

98

S E C T I O N 48

COMPENDIUM OF O R G A N I C SYNTiiETIC METHODS VOL 5

0 ($4

+

0

O,H,+,

CHO

Bu4d%l0 Synthesis

n-C7H15-CH20H

1) DEAD L-.

2 ) Ph3P

90%

394 (1981)

-n-C7H15CH0

(52%

T e t r L e t t , -22, 2295 ( 1 9 8 1 )

A

RuCl 2L3 ( CH2)0C1i20H

(CH2)2CH0

benzene Tetr Lett,

l-octanol

RuCl 2L3 PhIO o r P h I ( O A c ) 2

*

22,

89%

1605 (1981)

octanal

Tetr Lett, 22, 2 3 6 1 (1981)

9 7%

SECTION 4 8

ALDEHYDES FROM ALCOHOLS

0

t-BuOOH

CH3( CH2)8CH201i

i1

b

M

S

e

j

99

cii3( CH?)~-C-H

92%

2

:oc, 9, a37

(1922)

JOC, 4 7 , 1 7 2 7 (1932)

Cr03 PhM

CH20H

b

P.T.C.

Ph

WCH0 65%

Tetr Lett, 21, 4 6 5 3 (1980)

100

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 48

S y n t h e s i s , 646 (1920)

-n-Hx, Ple’

n-Hx,

( BU4N ) 2Cr$J7

C=CH-CH20H

-t

CH2C1

Me

,C=CH-CHO

7 6%

S y n t h Comm, 10, 7 5 ( 1 9 8 0 )

N Me I

L

JOC, 47, 1 7 3 7 ( 1 9 C 2 )

0

[ B z N E t 3 I 2 C r 2 0 70 PI1-CH,OH L

HFIPT

0

*

I1

Ph-C-H

Synthesis,

1091 ( 1 9 3 2 )

90%

SECTION 48

ALDEHYDES FROM ALCOHOLS

101

CH,OH

CHO

OMe

OMe

I

L

*PCC = pyridinium chlorochromate PDC = pyridinium dichromate JCS Perkin I, 1967 (1982)

Ph-CH20H

Fe(N03)3, HS

* bentonite clay

Ph-CHO

8 1%

Synthesis, 249 (19GO) OH

OH

CH20H

CHO JOC, 45, 1596 (1920) c

102

S E C T I O N 48

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

Ph-CH20H

C1 S02NC0 DMSO

90%

* Ph-Ct-10 S y n t h e s i s , 141 (1980)

Ph-CH20H

N i ( OBz)

92%

* Ph-CHO

Br2

0

Synth Comm,

10,881

(1980)

83% JOC,

46,

1927 (1981)

polymer-bound p e r i o d a t e

JCS P e r k i n I, 503 (1982)

90%

SECTION 49

103

ALDEHYDES FRCM ALDEHYDES

Ph-I

Pd( OAc)2

+

82%

w

Et3N Ph

Cjrg Syn,

R e l a t e d methods:

61,

82 (19G3)

Ketones , ,-omii coho1 s and Phenol s ( S e c t i o n

3)

S e c t i o n 49 Aldehydes f r o m Aldehydes C o n j u g a t e r e d u c t i o n s and M i c h a e l a1 k y l a t i o n s o f c o n j u g a t e d a l d e hydes a r e 1 i s t e d i n S e c t i o n 74 (A1 k y l s f r o m O l e f i n s )

Q

A 1) Me-N-N-Li 2) BuLi

e

3 ) CH31

4 ) H30t

.

qCH 61%

c1

c1

Tetr Lett,

23,

3979 ( 1 9 8 2 )

104

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

SECTION 49

aCHO c" ti

CHO

HOAc/ H20

f

OMe

262

S y n t h e s i s , 677 (1930)

Related methods:

A1 dehydes from Ketones ( S e c t i o n 57).

from Ketones ( S e c t i o n 177). Also v i a : ( S e c t i o n 341).

Ketones

O l e f i n i c aldehydes

S e c t i o n 50 Aldehydes from Alkyls

FH3

CHO DDQ

I

84%

CH30H bH

OH Org Prep Proc I n t , 1 2 , 201 (1980)

SECTION 5 2

ALDEHYDES FROM A M I N E S

105

4 CHO

( o r CuS04, S2O.g =p eY r couxIy1d i s u l f a t e ) OMe

70%

OMe

I n d i a n J Chem, 2 0 B , 153 ( 1 9 G l )

S e c t i o n 5 1 Aldehydes f r o m Amides No Addi t i o n a l Exampl es

.

S e c t i o n 5 2 Aldehydes f r o m Amines CHO

CH3

e-

DBU JACS, 104, 4446 ( 1 9 3 2 )

CHO

84%

COMPENDIUM OF O R G A N I C S Y N T H E T I C METHODS VOL 5

106

SECTION 52

0 It

YH2

100%

PhO'\H

DMF, D B U

7% (1982)

Synthesis,

Ph-CH2NH2

1)

pk

Ph 2) Me1

Ph-CHO

5 3%

3 ) A g C N , DMSO

Synthesis

1) CH3( C t i 2 ) 9 - C H 2 N H 2

,

711 (1981)

CHO

2) LDA

*

CH~(CH~)~-CHO

3) (COOH& MeOH/THF/H20

JOC,

$6, 1937

(1981)

94%

SECTION 52

ALDEHYDES FROM

AMINES

107

N-S-Ph I

29% JOC,

46,

4617 (1931)

1) H202, CH30H U

2 ) Ac20

H

CH 2NMe2

O

60% Chem L e t t , 1987 (1982)

Ph2Se( OCOCF,), Me0

DME

* M e o m Me0

20% JACS, 103, 4642 (1981)

X e l a t e d methods:

S e c t i o n 172 ( K e t o n e s from Amines).

108

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 53

Section 53 Aldehydes from Esters

No Addi tional Examples

.

Section 54 Aldehydes from Ethers

Bu-CH2-OBu

Cl

Bu-CHO

w

2) H30t

~30%

-

Aust J Chem, 32, 2787 (1979) 1

p,

PrCH2

/ '

TMS

Pd(OAc)2

DMF

~

Pr

93%

CHO

Chem L e t t , 1997 (1982) Related methods:

Section 174 (Ketones from Ethers a n d Epoxides).

SECTION 55

ALDEHYDES FROM HALIDES

109

S e c t i o n 55 Aldehydes from H a l i d e s

0 II

H-C-OMgBr t

2 ) H20

* EX-CHO

75%

Hx-MgBr

Tetr L e t t , _2_1, 2869 ( 1 9 3 0 )

9 1%

Bull Chem SOC J a p a n ,

22,

1663 ( 1 9 5 2 )

72%

Angew I n t Ed, ?O-, 373 (1921)

110

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

S E C T I O N 55

0 i1

n-C9H19MgBr

-n-CgHl9-C-D

2 ) HgO, HBF4

G8%

TH F/H20 T e t r L e t t , 22, 1321 ( 1 9 8 1 ) c

1) Me2N * --0

*

n-C8H 7C1

n-C7H15CH0

88%

2 ) DBU B u l l Chem SOC Japan,

24,2 2 2 1

(1981)

1) PhS?HSiMe3

n-Hx-Br -

2 ) MCPBA, A

3)

H308

* n-Hx-CHO

65%

I

overall Tetr Lett, 21, 1677 ( 1 9 3 0 )

SECTION 5 5

ALDEHYDES FROM HALIDES

111

0

1) P h A C O O M e 2 ) NaOH, MeOH

Bu-CH2Br

*

3 ) NaBH4, E t O H

4 ) Pd(OAc)2,

Bu-CH2CH2 CHO (heptanal )

I,, benzene

%50%

L

-

I n d i a n J Chem, 21B, 403 ( 1 9 8 2 )

1) ( E t O C H = C H k B

NaOH, PdL4 2 ) n30+ /C-CH

'0

-

JOC, 47, 2117 (1982)

tig(OAc)2, TFA

- 10 2 1CH=CHF

H20, NatiC03

*n-C n cti CHO 10 2 1 2 Chem L e t t , 6 5 1 (1980)

95%

112

C O M P E N D I U M OF O R G A N I C SYNTHETIC METHODS VOL 5

Bu-CBr2Li t

0 I1

H - C - OMe

2 ) H3@

-

SECTION 55

78%

Bu-CBr2-CH0

may a l s o b e used t o form z-monohalo a l d e h y d e s S y n t h e s i s , 644 ( 1 9 3 0 )

Ph-I t

Pd ( OAc)

82%

Et3N Ph

Org Syn,

61,

82 ( 1 9 3 3 )

S e c t i o n 5 G Aldehydes from tiydrides

Synth Conirn,

12, 435

(1932)

SECTION 56

Review:

ALDEHYDES FROM H Y D R I D E S

113

"The Reirner-Tiernann Reaction:

Org React, -23, 1 (1932)

@CH ( OE t )

87%

-i -Pr2NEt JOC,

46,

2557 (1931)

b

1) PhSeTMS, TMSOTf 2 ) HC(OEt)3, TMSOTf

C H ( OE t )

*

76%

Tetr Lett, -22, .1809 (1931)

1)Me2NCH0, P 0 C l 3 2 ) H20, NaOH

Me

0 I

Me

Org Prep Proc I n t ,

3,97

CHO

(1981)

95%

114

C O M P E N D I U M OF O R G A N I C SYKTHETIC METHODS VOL 5

SECTION 57

S e c t i o n 57 Aldehydes from Ketones

6 6

97%

U

2 ) H202, NaHC03

JOC, 4 5 , 1091 ( 1 9 3 0 ) c

I. i

1) Ph2PtkOCti3 2 ) MeOH 3 ) CH31 4 ) C1,CCOOH

Ib CHO

9 14

. I

T e t r Lett, 21, 3535 ( 1 9 8 0 ) c

Helv C h i m A c t a ,

63,

1665 ( 1 9 8 0 )

SECTION 57

(To t

A OE t

ALDEHYDES FROM KETONES

1) montrnorillonite clay 2) Ht

-

115

W

C

\I

H

O

50%

Synthesis, 137 (19G1)

0

H

I1

( MeO) 2PCHN2

I

c

\

N O H y -t-EuOK

Tetr Lett, 21, 5003 (1930)

Synthesis 45 ( 1980)

O

V

60%

116

COMPENDIUM OF O R G A N I C SYKTHETIC NETHODS VOL 5

SECTION 58

S e c t i o n 58 Aldehydes f r o m N i t r i l e s

00 1) E t 3 0 BF4 C -E

N

2) E t 3 S i H

*

M

3 ) H20

71% JOC, 46, 602 (1981)

JOC, 46, 3372 (1981) I

B u - CH C N

1) DIBAL-H

2 ) LDA, HMPA

CHO

* Bu-CH-CHO I

‘gHll

3 ) C5ti11Br

JOC,

_4T, 5250 (1981)

SECTION 59

ALDEHYDES FROM OLEFINS

117

Section 59 Aldehydes from Olefins

-

1) Sia2Bk

2 ) PCC

67%

W C H O

Synthesis , 151 (1930)

(BiPy)H2CrOC15 Ph

t

2 Ph-CHO

Ph

Org P:-op Proc I n t ,

Review:

"Ozonolysis

--

14,362

(19%)

A Modern Method in the Chemistry of

Olefins" Russ Chem Rev,

Rev iew :

"

20,636

(1931)

Asymme t r i c Hydro f ormy 1 a t i on " Topics in Current Chern, =,77

Related methods:

Section 179 (Ketones from O l e f i n s )

(1982)

118

COPIPENDIUM OF O R G A N I C SYNTHETIC METHODS V O L 5

SECTION GC

S e c t i o n GO A1 dehydes from M i s c e l l aneous Compounds

CH ( CH2 ) c-CH21102

0

1) NaH

i1

CH3( CH2)c-C-H

2 ) KMn04

922

JOC, 47, 4534 (1932)

C t i ( CH )

- CH NO

H202 Y K p 3

+

MeOH/H20

CH3( CIi2)4-CH0

S y n t i i e s i s , 44 and 6 6 2 (1900)

7%

1) NaH, t-BuOH

CH2N02

2 ) KMn04

CN

JOC, 47, 4534 (1982)

30 Z

SECTION 60A

PROTECTION OF ALDEHYDES

119

I

-t-BUOH

CN

CN

JOC,

46,

74%

1037 (1981)

9

S e c t i o n 60A P r o t e c t i o n o f Aldehydes

A

OTllS

R’

0 II

R-C-H

0

‘c’H‘ 0

T f OTMS

\

>90% y i e l d s

MeOTMS

T f OTMS

MeO\

R’ Tetr Lett,

C

/ OMe

‘H

3,1357

(1920)

120

COMPENDIUN OF ORGANIC SYNTHETIC METHODS

Ac20

R-CHO

N a f ion-H

R = a1 k y l , a r y l

~

SECTION QOA

VOL 5

OAc

R\

/

H /c

\oAc

50-99%

, h e t e r o c y c l ic S y n t h e s i s , 962 (1982)

-

0 II

R'

C H'

R" = a l k y l

,

2R"SH

S R I.'

A1 C1

H

..loo%

dithiol Tetr Lett,

n

s\ R

2

0k

H

( PiiSeO) 2O

2,4225

(1930)

0 ,I

w

R'

JCS P e r k i n

C

'ti

I , 1654

(1933)

S E C T I O N 60A

n

s.\c /s

‘H

R’

PROTECTION

Me3Si I ( o r B r ) DMSO

OF ALDEHYDES

121

0II

65-99%

* R/‘\H S y n t h e s i s , 965 (19G2)

n s\ f?’

C

0S

H‘

HC1 , H20/DMSO/dioxane

U

I1

w

R/c\

or MeS(SMe)2 %bC16 0

H

>95%

S y n t h e s i s , 679 (1982)

n

s\ ,s R’

C

‘H

e l ectrochernica 1 o x i d a t i o n ( e - 7 0 1 ) 3N

0I1

* R’

C

‘H

T e t r L e t t , -21, 511 (1980)

35-97%

122

COMPENDIUM

N’

OH

I1

t

C H‘

SECTION 60A

0

N a 2S O4

I1

’R

OF ORGANIC SYNTHETIC METHODS VOL 5

H2°

H A u s t J Chem, 32, 201 ( 1 9 7 9 ) I _

1) VC12

77?

2) H30f

S y n t h e s i s , 220 (1980)

7 0- 90 %

X = OH, NHPh

H C=C, 2

/ CHO

CH3

Ac20, PC13

JCS P e r k i n

I,

-

C,H

ti

2

c=c,

1212 ( 1 9 8 0 )

( OAc) 2 cti3

S y n t h e s i s , 024 (19G1)

SECTION 60A

PROTECTION OF ALDEHYDES

-

I

1)

Li

k-CHO 2 ) Me3SiC1

S t a b l e t o R ' L i and workup.

R'MgX.

123

,N-Me

TMSO,

R

C 0 \

H

D e p r o t e c t i o n o c c u r s d u r i n g t h e normal

-

T e t r L e t t , 22, 4213 (1921)

See S e c t i o n 367 ( E t h e r

-

O l e f i n ) f o r t h e formation o f enol ethers,

Many o f t h e methods i n S e c t i o n 180A ( P r o t e c t i o n o f Ketones) a r e a l s o a p p l i c a b l e t o aldehydes.

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 5 PREPARATION OF ALKYLS, METHYLENES, AND ARYLS

This chapter l i s t s the conversion o f functional groups into Me, Et CH2, P h , e t c .

...,

Section 61 Aryls from Acetylenes

0

0 57%

Synthesis , 29 (1930)

xcocl H-CEC-CH 3 A1 C1

Tetr L e t t ,

)& 3, 4923

(1982)

69%

SECTION 63

125

ALKYLS FROM ALCOHOLS

S e c t i o n 62 Alkyls and Methylenes from Carboxylic Acids

0 I1

2 MeO-C- ( C t i , ) 4COOH

anodic o x i d a t i o n MeOli, NaOMe

0

0

60,

1 (1931)

II II * MeO-C-(Cti2)3-C-OMe

Org Syn,

712

S e c t i o n 63 Alkyls from Alcohols

OH

Ph-bH-Ph

S-

i Me 3’ B F 3

+ P h-C ti- P h

JOC, 4 7 , 2125 (1982)

1009

126

SECTION 63

C O M P E N D I U M OF O R G A N I C S Y N T H E T I C METHODS VOL 5

Chem L e t t , 157 (1982)

T e t r L e t t , 2 2 , 4449 (1901) 1

S e c t i o n 64 Alkyls from Aldehydes

Ra-Ni H20/ EtOH dOOH

-8 tH3

CHO

COOH

Tetr Lett,

1, 2637

(1980)

69%

SECTION 68

A L K Y L S , METHYLENES, AND ARYLS FROM ESTERS

127

Re1 a t e d methods : A1 kyl s , Methyl enes , and Aryl s from Ketones (Section 72)

S e c t i o n 65 Alkyls and Aryls from Alkyls and Aryls

PhLi, TMEDA

66%

TH F

Ph

JACS,

102, 6519

(1920)

S e c t i o n 66 A1 kyls , Methyl enes , and Aryl s from Amides No Additional Examples

.

S e c t i o n 67 A1 kyls , Methylenes , and Aryls from Amines No Additional Examples,

S e c t i o n G O A l k y l s , Methylenes, and Aryls from E s t e r s

128

COMPENDIULI OF O R G A N I C S Y N T H E T I C METHODS V O L 5

S E C T I O N 68

0

n

'Tetr Lett, 21, 3237 (1930)

LiCl

64%

HMPA J C S C h e m Comm, 30 (1931)

.COOMe

Ph

4

Ph

~

&ph

c-p11

t-BuOK 72% Tetr Lett,

ZL, 5097

(1981)

SECTION 69

ALKYLS A N D A R Y L S FROM ETHERS

Ph

OAc

129

PdL4 +

t

Ph

PHF

SnBu3

69% Tetr Lett,

z, 2591,

2595, and 2599 (1980)

S e c t i o n 69 Alkyls and Aryls from Ethers The conversion ROK section,

+

R R ' ( R ' = a l k y l , a r y i ) i s included i n t h i s

Ti (O)/Ti ( 1 1 ) TH F OMe

OMe

GO%

Ph

CH3

JACS, jg, 426 (19CO)

C O M P E N D I U M OF O R G A N I C SYNTHETIC NETHODS VOL 5

130

&$

SECTION 69

&)

F

F

CF3COOH NaBH4

97%

Me

Me

S y n t h e s i s , 143 (1922)

t-BuOC-CH2MgC1 0 I1

t-BuOC-CH2-CH-NMe2 I

t

76%

Ph

BuO-CH-NMe2 I Ph Bull Soc Chim France 1 1 , 395 (1932)

S e c t i o n 70 A1 kyl s and Aryl s from Hal i d e s The replacement o f halogen by a l k y l o r a r y l groups i s included i n this section.

For t h e conversion RX

-f

Rti ( X = h a l o ) s e e S e c t i o n

160 (Hydrides from tial i d e s and Sul f o n a t e s ) .

SECTION 70

ALKYLS AND ARYLS FROM HALIDES

131

70X

JCS Chem Comrn, 1202 ( 1 9 0 0 )

Bu

Angew Chem I n t Ed,

Ph,CH

-

P hC ti2L i

Ho-

c1

2,900

cti

and 301 (1980)

*

THF

PhCH2 JOC, 117, 300C ( 1 9 0 2 )

20%

1) LiCH2TePh R-X R =

2 ) S02C12, B r 2 , or I2 3 ) l o o o , OMF

+

R-CH2X

'1 a l k y l Chem L e t t , 1081 (19C2)

5 9- 95%

132

C O M P E N D I U M OF O R G A N I C S Y N T H E T I C METHODS VOL 5

S E C T I O N 70

t-BuLi

I

9 7%

Tetr Lett,

H3C

alx

BuLi

23,

5123 (1902)

- $Jo7

Br

73%

H3C

JOC, 4 6 , 1384 (1981)

-

COCl L3

2 (Also works with '1 and 2'

benzene

benzyl c h l o r i d e s . ) Chem L e t t , 1277 (1931)

33%

SECTION 70

133

ALKYLS AND ARYLS FROM HALIDES

OBr

-SnBu3 AIBN

104, 5329 ( 1 9 8 2 ) JACS, --

(y

CH,CH=CH2 Br

1) Bu2CuLi

96::

2 ) -r

L

Bull Chem SOC J a p a n ,

Tetr Lett,

z,3632 ( 1 9 7 9 )

_22, 2715

(1981)

134

C O M P E N D I U M OF O R G A N I C S Y N T H E T I C METHODS VOL 5

Hx-CH=CF,

S E C T I O N 70

BuLi

Et20

76%

HxCHZCHBU

C h e m L e t t , 935 ( 1 9 8 0 )

1) B u L i

/ cti3

B u l l SOC C h i s 1 F r a n c e I 1

2Pli- B r

Ni ( C O D )

297 (1932)

02%

Ph-Ph

D P1. F Ph

70%

JACS,

203,

6460 (1931)

SECTION 70

ALKYLS AND ARYLS FROM HALIDES

CH3MgBr

H SO2 -t-B u

+

N i (acac)?

135

H

W80%

cti3

Tetr Lett, _?3,2469 (1982)

Bu2CuLi

w

Bu zB&

81%

PhS02 JCS Chem

Comm, 434 (1980)

Organometall i c s , J,, 259 (1932)

136

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 70

JOC, 47, 1 6 4 1 ( 1 9 2 2 )

n

THF

LPr n

PrMgBr, L 2 N i C 1 2

*

a

JOC, 47, 4319 ( 1 9 2 2 )

Q

p”. 0

Q

60%

Cti2CF3

CH2Br

N02

cF3

same condi.tions

n02

S y n t h e s i s , 932 ( 1 9 8 3 )

52%

S E C T I O N 70

137

ALKYLS AND ARYLS FROM HALIDES

q1 CH 3

CF3C02Na CUI

*

qCF 83%

cii Chem L e t t , 1719 (1981)

4

JCS P e r k i n

I, 3007 ( 1 9 8 2 )

T

1

+

Ph S nMe

83%

Ph JOC ( U S S R ) , 17, 18 (1981)

138

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 5

-

SECTION 70

H2NNt12

Pd-Hg

Ph-Ph

90%

B u l l Chem SOC Japan, 5 3 , 1767 ( 1 9 3 0 ) I

a c t i v a t e d Ni

c

35%

Tetr Lett, 23, 4 2 1 5 ( 1 9 8 2 )

OMe

PhPdIL2

+

9 7%

B u 4 N I , HMPT * 2 @

B u l l Acad USSR Chern,

2,1993

(1982)

SECTION 70

ALKYLS AND ARYLS

FROM

HALIDES

139

MgBr

C

l

V c1 69%

OMe OMe JOC, 46, 2194 (1921) c

Li 2CuC1 b

c1

U

35%

Tetr Lett,

3,3115

(1932)

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

140

C'

N

:

Me

CN

S E C T I O N 70

X C N

92%

CN

Br A c t a Chem Scand B, 34, 209 (1980)

OCH3 P h L i , TMEDA

66%

c1

*

TH F JACS,

Review:

O

P

_1g, 6519

h

(1980)

"The s y n t h e s i s o f s u b s t i t u t e d c y c l o p r o p a n e s and c y c l o propenes by t h e r e d u c t i v e c y c l i z a t i o n o f p o l y c l . i l oroa1 kanes ,"

Russ Chem Rev, -51, 362 (1982)

hw

70%

Bu4Sn OH

CN

-

CN

JACS, 104, 2321 (1982)

SECTION 71

ALKYLS AND ARYLS FROM H Y D R I D E S

141

S e c t i o n 7 1 Alkyls and Aryls from Hydrides This s e c t i o n l i s t s examples o f t h e r e a c t i o n RH + R R ' ( R , R' = a l k y l o r a r y l ) . For t h e r e a c t i o n C=CH + C = C R ( R = a l k y l o r a r y l ) s e e S e c t i o n 209 ( O l e f i n s from O l e f i n s ) . For a l k y l a t i o n s o f ketones and e s t e r s , s e e S e c t i o n 1 7 7 (Ketones from Ketones) and S e c t i o n 113 ( E s t e r s from E s t e r s )

.

Ph-NH2 , L-BuONO Pd( dba)2

*

hPh78%

u

JOC, 46, 4385 (1981)

2 2 , 7C3 (1981) l e t r Lett, 2 Ar-H

T1 ( T F A ) 3

T FA Ar = s u b s t . P h

w

Ar-Ar widely v a r y i n g y i e l d s

-

JACS, 102, 6504 (1980)

142

CONPENDIUP~I OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 7 1

1) PhCH2CH2MgBr 2 ) H20 3 ) KMn04,

62%

HO'

OMe

OMe JOC,

$5,522

(1980)

TMC II'IJ

N

67%

T1 ( T F A ) T e t r L e t t , 22, 4 4 9 1 ( 1 9 8 1 ) A

9 CHO

c1

A

1) Me-N-N-Li 2) BuLi 3 ) CH31 4 ) H3@

v3 ctio

61%

c1

-

T e t r L e t t , 23, 3979 ( 1 9 8 2 )

q

SECTION 71

A L K Y L S AND A R Y L S FROM H Y D R I D E S

0

143

0 SnCl

30%

benzene

OMe

OMe

T e t r L e t t , -21, 1837 (1930)

1) CH3MgX 2 ) O' H

-

&cti3

60%

NaOCl

ti20/E tOH S y n t h e s i s , 616 (1980)

Ph I

1) 5% C U I

2 ) EtOCOCl

77%

3 ) PhMgBr

J O C , 47, 4315 (19G2) c

144

C O M P E N D I U M OF O R G A N I C SYNTHETIC METHODS V O L 5

SECTION 71

T1 ( T F A ) 2

9 3%

Pd ( OAc)

( b a s e d on T 1 )

CH3

Tetr Lett,

z,3793 (1981)

1) BrMg CH2 1 4MgBr

54%

2 ) Jones

JOC,

92,1822

JACS,

(1920)

102, 1602

(1980)

SECTION 72

ALKYLS, METHYLENES, A I ~ DARYLS FROM KETONES

145

S e c t i o n 72 A1 k y l s , M e t h y l e n e s , and A r y l s f r o m Ketones The c o n v e r s i o n s R 2 C 0 + R R ,

R2CH2,

R,CHR', L

section.

etc. are l i s t e d i n t h i s

1) H 2 N N H T s , E t O H 3) RaOAc, H20 J O C , -4 6 , 1217 (1901)

8 OT f

TFAA

*

Pt02 HZ

*

0

Tetr Lett, 23, 117 (1982)

JOC, 4.5, 3393 (1980)

90%

146

COMPENDIUM

0

OF O R G A N I C S Y N T H E T I C METHODS VOL 5

Ra-Ni

I/

P h -C- CH

H,O/ L

SECTION 7 2

9 49:

PhCH2CH3

Et O H

Tetr Lett, 21, 2637 (1980)

"*C

-CH

CH2CH3

&

NO2

92%

CH2C1

Org Syn,

Ph2C=0

I

E t 3 S i H , BF3

NaBH4-PdC1 LleOH

*

60,

108 (19C1)

Ph-CH2-Ph

C h e m L e t t , 1029 (1931)

J C S C h e m Comm, 237 (1981)

S E C T I O N 72

ALKYLS, METHYLENES, AND ARYLS FROM KETONES

147

OMe

1) BrMg 2 ) L i , NH3

0

Ph JOC, 46, 5060 ( 1 9 8 1 )

1 ) H2NNHTs, E t O t i 83%

2) (PhC02)2BH

3) NaOAc, H20 JOC, 46, 1217 ( 1 9 8 1 ) I

-& OH

OTMS Ph3C@

L i e b i g s Ann Chem, 533 ( 1 9 8 0 )

93%

148

C O M P E N D I U M OF O R G A N I C S Y N T H E T I C METHODS VOL 5

S E C T I O N 72

(Yo xo 1) L D A

2)

SPh

3) TsOH JOC,

47,

1200 ( 1 9 8 2 )

Q-- PHO n

CH 3

KOti

CH30H

96%

t

Tetr Lett, 23, 2223 (19G2)

1) M e 3 S i C 1 , E t N 2) ( ! T H O H

-p

3

PlgCl

3 ) H30@ 4 ) T s O H , benzene JOC,

47,3163

B

( 1922)

81%

SECTION 74

A L K Y L S , METHYLENES, AND A R Y L S FROM OLEFINS

149

S e c t i o n 73 .. A l k y l s , Methylenes, and Aryls from N i t r i l e s

&

CN

HZ

92%

Ni/A1 203 Synthesis

302 ( 1980)

10% Pd-C

H C O @~ N H ~

HO

Synthesis

HO 1036 ( 1982)

S e c t i o n 74 A l k y l s , Methylenes and Aryls from O l e f i n s The f o l owing r e a c t i o n types a r e included i n t h i s s e c t i o n : A.

Hy r o g e n a t i o n of o l e f i n s (and a r y l s ) .

B.

Formation o f a r y l s ,

C.

A l k y l a t i o n s and a r y l a t i o n s o f o l e f i n s .

D.

Conjugate r e d u c t i o n s of conjugated aldehydes , k e t o n e s , a c i d s , e s t e r s , and n i t r i l e s .

E.

Conjugate a i k y l a t i o n s .

r

Cyclopropanations, i n c l u d i n g h a l o c y c l o p r o p a n a t i o n s .

r.

100%

150

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

74A:

SECTION 74A

Hydrogenation o f O l e f i n s ( a n d a r y l s )

NH20H, EtOAc DM F

C 7 H 15CH=CHCH20H

CH CH CH OH *C7H15 2 2 2

Synth Comm,

12,287

(1982)

0

H2 (>lo00 p s i )

JOC, 45, 1418 (1930) I

H2

, H20/tol uene

K3[Co( C N ) 5 H ]

w

P.T.C.

JOC, 4 5 , c

96%

3860 (1980)

70%

SECTION 74A

151

HYDROGENATION OF OLEFINS (AND ARYLS)

a 1%

t o 1 uene

55, 343 ( 1 9 3 2 ) B u l l Chert1 S O C Japan, -

JOC, 45, 1937 ( 1 9 2 0 ) -I

[Rh( 1 , 5 - c o t ( R Y R ) - d i - P A M P ) ]

0

*

CH

x / CF 3 -CH ‘OAc

100% JOC,

-L

45,

1 1 2 (30 atm) s i l ica-bound Rh-phosphi ne c a t a l y s t

77% ee (S)

2362 (1920)

-0 4-

Chem L e t t , 603 ( 1 9 2 2 )

9 6%

152

COMPENDIUM

OF

ORGANIC SYNTHETIC METHODS VOL 5

SECTION 74A

JACS,

H2

102, 5948

70% (1980)

&

/

Y+/yy00 4

C

JOC,

97'0

115,

95"9

2797 (1980)

748: Formation of Aryls

Synth

Comm,

12,G37

(1982)

SECTION 74D

CONJUGATE REDUCTIONS

153

46-707;

X = 0 , C H 2 , ldMe

Tetr L e t t ,

Y = 0 , CH2

74C:

n

(1930)

A l k y l a t i o n s and A r y l a t i o n s o f O l e f i n s

JACS,

74D:

1, 839

JE, 5955

(1980)

Conjugate Reductions

0

JCZ Chem Comrn, 1013 ( 1 9 3 0 )

154

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

b

SECTION 74D

1i2 , H20/ t o 1 uene 75%

K3Ko ( CN) 511 1 P.T.C.

JOC,

_42, 3860

(1980)

Organometall i c s ,

1,1590

(1982)

Me

Me

Ph

-

N3

77%

HeOH

H

H

COOH

JCS P e r k i n

Na2S204

+

I , 2 9 1 2 ( 1961)

w

P.T.C.

Chem L e t t , 715 (19G2)

COOH

6 3%

SECTION 74D

155

CONJUGATE REDUCTIONS

0

'

S y n t h e s i s , 400 (1980)

B u L i , CuI Bu3P

0

c

2~

-t T

0

L- CH

-

0

93%

Bu

Tetr Lett,

zl-, 1247 (1920)

Tetr Lett,

g,303

N a I , iiC1 acetone

-

0

(1931)

0

C12H25-t<E-CH3

S y n t h e s i s , 245 ( 1 9 0 0 )

100%

156

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

0 COOH Ph

NH20H , C H 3 - C - O t t

COOH w Ph

w

D 1.1F

6 7%

S y n t h Comm,

0 Ph

HFe( CO)? TliF

12, 237

wCHo

Ph

3,1329

BuSnH

>98%

(1932)

CHO

T e t r L e t t , -23,

477 ( 1 9 3 2 )

-nA 0

HCOONa PhdPh

(1982)

- A

B u l l Chem SOC Japan,

Ph

SECTION

RuC12L3, P.T.C.

Ph

22, 1709 ( 1 9 5 1 ) T e t r L e t t , _-

Ph

74E

SECTION 74D

CONJUGATE ?EDUCTIONS

C0,Bz Ph

W

NaHTe

157

C02Bz

+

L

Ph

w

Chem L e t t , 847 (1980)

0

0

1) DIBAL-H

Me0

2 ) 14eOti

Me 0

S y n t h e s i s , 574 (1981)

CuBr/Vi t r i d e butanol /THF

JOC,

45,

6

167 (1980)

90%

92%

153

COMPENDIUFI

Ph2C=C,

,COOE C 14

t

OF O R G A N I C SYNTHETIC METHODS VOL 5

L DA

TH F

P h C H- CH,

YCOOEt

Me

MeOH

81%

CN

JCS P e r k i n

Mg

S E C T I O N 74D

I , 1267 (19CO)

Me

-

Me

Tetr Lett, 2 l-,

w-B 0

6 1%

2915 (19CO)

..lr = s u b s t . Ph

my

>go% >90% ee

Chem B e r , 2323 ( 1 9 8 0 ) JOC, 45, 5137 ( 1 9 8 0 ) Chem Lett. 7 ( 1 9 8 0 ) JACS, 98a (1930) S y n t h e s i s , 7G ( 1 9 8 1 ) JOC, 46, 2954 and 2960 ( 1 9 3 1 ) JACS,T03, 2273 ( 1 9 8 1 ) J C h e m T s ( S ) , 117 ( 1 9 8 2 )

102;

SECTION 74E

74E:

CONJUGATE ALKYLATIONS

159

Conjugate A l k y l a t i o n s

6

ile5Cu3Li2

CH3

CHO

90%

Et20

JCS Chern Conini, 643 (1981 ) J3C, 47, 2572 ( 1 9 8 2 )

Me

0

'Ph

88% S14 ee

Ph

Cken L e t t , 45 ( 1 9 8 9 )

1 ) C597Cu-HMPT, L i 3u3r

3

''6 sonication

91 %

0

sonication

JOC, 47, 3805 (1982)

160

COMPENDIUM OF ORGANIC S Y N T H E T I C METHODS VOL 5

PhHgCl

SECTION 74E

85% Tetrahedron, 37 , 2941 ( 1981 1

Y

M93r

, CuBr(Me,S)

+ 2 ) H C 1 , H20

0

.75% overall JCC, 47, 5045 ( 1 9 8 2 ) I

0

Can J Chem, 50, 94 ( 1 S 8 2 )

SECTION 74E

CONJUGATE ALKYLATIONS

n

161

-t-Bu

%0,Me

N

I1

1 ) 'eM

C

1

'CH2+CuLi

*

2) H30t

89%

75% ee

Tetr Lett, 23, 3711 ( 1 9 8 2 )

1)

+cm

Cp2ZrC1H

2 ) uO

3 ) H3@

m

0

78%

, Ni(I1)

JACS, __ 102, 1334 ( 1 9 8 0 )

1 ) Li /NH3-THF

2 ) CH31

-Lo O

- --

= H

CH3

66%

6H

JACS, 102, 1218 and 1219 ( 1 9 8 0 )

162

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 74E

Tetr Lett, 21, 3237 (1980)

NMe2

B u LBi r

N

- J&

NMe2

90%

CH2CH=CH2

-

T e t r L e t t , 21, 4823 (1980)

0

-

Ph

T e t r L e t t , 23, 5531 (1982)

0

SECTION 74F

CYCLOPROPANATIONS

163

0

99% ee

Chem Lett, 913 ( 1 9 8 1 )

NaBH4

AcO 72%

H2C=CHCN Angew Chem Int Ed, 21, 130 (1982) 74F: Cyclopropanations

Me

Synthesis, 714 (1981 1

164

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 74F

JACS, __ 103, 1862 (1981)

CH3CH I 2

'

H

Zn-Cu, ether

-

63%

H3CH@oH H

JOC, 47, 1615 (1982)

0 I1

Ph-CH=CH-C-Ph

0

I:Me3fC H -C N ]

0 I1

* Ph-CH-CH-C-Ph

\/

61 % trans:cis

S y n t h e s i s , 301 ( 982) EtOOCCHN2 Lc

Rh, Cu catalysts

COOEt 88%

JOC, 45, 695 and 1538 (1980) T e t r L e t t , 2 2 , 1783 (1981)

S E C T I O N 74F

CYCLOPROPANATIONS

Cu2Br2

165

COOEt

71 %

-I

DMSO

COOEt

Br2C ( C O O E t 1

B u l l Chem SOC Japan, 54, 2539 (1981)

COOEt

1 ) MeSSMe, S02C1

62%

2 ) NaCH(COOEt)2

3 ) (Me0)2S02

4) NaOEt

COOEt

's0

S y n t h e s i s , 690 ( 1 9 8 0 )

o ~ ( ~ ~. ~

11. e 0 H,%

0

C-CHN2 I1

0

H

85% I n d i a n J Chen, 20B, 911 (1981)

166

COMPENDIUPI

OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION

Section 75 Alkyls and Methylenes from Miscellaneous Compounds

1) 2)

3)

N02

Jr THF

AcOH, H 2 0

tp, MeCH

Synthesis, 836 ( 1 9 2 2 )

Cliem Lett, 1 2 0 9 (1920)

-

TiC14 CH ( OMe)

To1

To 1

Tetr Lett, 2 2 , 3335 (1981)

45%

73%

59%

75

S E C T I O N 75

A L K Y L S A N D M E T H Y L E N E S FROM M I S C E L L A N E O U S

167

COMPOllNDS

0

O I1P ( O E t ) 2

IixMgB r w

63% J C S C h e m Comrn,

2G5 (1932)

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 6 PREPARATION OF AMIDES Section 76 Amides from Acetylenes

No a d d i t i o n a l examples Section 77 Amides from Carboxylic Acids, Acid Halides, and Anhydrides

H2N( Cti2)5COOH

a1 umi na

32%

o r s i l i c a gel H

Tetr Lett,

2,2443

(1980)

A

ti,,N( C H 2 ) 5COOH L

>95%

Bu2Sn0 JAG,

102, 7578

(1980)

SECTION 77

Pr

AMIDES FROM CARBOXYLIC ACIDS, ACID HALIDES, AND ANHYDRIDES

-

MeS02C1 , CtiC1

'f' HNBz

COOH

H20, P.T.C.

3

Pr /N

BZ

169

0

Chem Lett, 443 (1981) 1) CH3S02C1

2 ) NH3

CH3( CH2) 16COOH

0 II +CH3(CH2) 16C-NH2

3 ) CH3S02C1

6 6

78%

Org Prep Proc Int, 14, 396 (1932)

1) C1S02F, Et3K

O=C-NH

G 1%

EtjN

2,

Synthesis, 661 (1980)

1) C1S02NC0, Et3N

P h - COOH

82%

Synthesis , 506 ( 1982)

170

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

SECTION 7 7

PI1 ( CH2) 3COOH

+

94% CH3

Ph,

CHNH2

0

Chem L e t t , 3 9 1 (1980)

CH3

0 I1

c-c1 1)

07HNPh

0

Q L1

N

H

~ %75%

N02

N02

B u l l SOC C h i m F r a n c e I 1 , 167 ( 1 9 8 2 )

0 11

+

-Y\/'NNH

(3 NH2

Ph3P, E t 3 N

Synthesis , 287 (1931)

h

SECTION 7 7

AMIDES FROM CARBOXYLIC ACIDS, A C I D HALIDES,

171

AND ANHYDRIDES

0

C5H l-COOH

0

2 ) BzNH2 S y n t h e s i s , 933 ( 1 9 8 2 )

-

COOH

w t

P h- CH CH3

-

KOH, Bu4@ H S P ,

!f

Ph 0

o p 2

I

0 11

Ph 1

C-NH-CH

;ti3 89%

N02

NH 2 Chem L e t t , 2 8 5 (1981)

Ph3P( OCH2CF3)

0 11 CH3C-NHBu

t

2) BuNH2 CH 3COOH JOC,

42,

5 0 5 2 (1920)

30%

172

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 77

0

POoH

1) ClbiPh2 2) H2NCH2CH2Ph

) J y - p h H

94% S y n t h e s i s , 335 (1980)

Ph-0-P,

!flHPh

may b e used as a c a r b o n y l - a c t i v a t i n g g r o u p f o r c1 t h e s y n t h e s i s o f amides a n d a n h y d r i d e s f r o m c a r b o x y l i c a c i d s . Y i e l d s a r e >90% S y n t h e s i s , 283 (1982)

0,

0

0

O''\Pr

i n peptide synthesis.

No s p a r i n g l y s o l u b l e

s e c o n d a r y p r o d u c t s a r e formed. Angew Chem I n t Ed,

19, 133

(2980)

D i p h e n y l p h o s p h o r a z i d a t e (DPPA) a n d d i e t h y l phos p h o r o c y a n i d a t e (DEPC) can s e r v e as coup1 i n g r e a g e n t s f o r sol i d - p h a s e p e p t i d e s y n t h e s i s i n DMF. Chem Pharm B u l l ,

S, 3064

(1980)

SECTION 7 7

AMIDES FROM C A R B O X Y L I C ACIDS, A C I D H A L I D E S ,

173

A N D ANHYDRIDES

Use of SDPP i n p l a c e of DCC f o r p r e p a r a t i o n o f a c t i v e e s t e r s in peptide synthesis.

T e t r Lett,

1, 1467

(1930)

Use of NDPP as an a c t i v a t i n g r e a g e n t i n t h e mixed anhydride method o f p e p t i d e s y n t h e s i s . n

0

JCS Chem Comm, 1029 (1930)

Use o f polymeric N-hydroxysuccinimide (NHS) as a coup1 ing agent in peptide synthesis.

Yields a r e ~ 9 0 % w i t h l i t t l e race-

mi za t i o n . Acta Chem Scand B y 23, 311 (1979) Use o f phenyl tetrazolinethionc/isocyanide as an a c t i v a t i n g group f o r p e p t i d e formation.

Yields a r e 60-84%, w i t h o u t race-

mi z a t i o n .

Angew Chem I n t Ed,

21,143

(1902)

174

SECTION 77

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

Use of t h i a z o l i n e - 2 - t h i o n e as a c a r b o n y l - a c t i v a t i n g r e a g e n t f o r peptide synthesis.

HN AA1- COOH

i

S I

0 * AA1-C-N

4\ u S

ti2N-AA 2

0 i1

AA1-C-NH-AA2

Chem Pharm B u l l , 2J, 314c) (1980)

+

R-C-NHR'

R ' - NH2

Allows p e p t i d e s y n t h e s i s u s i n g u n p r o t e c t e d amino a c i d s . JACS, 102, 4537 (1930) ~

0

T o

0

0

I1

H2N-C-NH2

* A

Synth Comm,

Related methods:

-sNH

(

T

11,447

Amides from Amines ( S e c t i o n 22)

82% 0

(1931)

S E C T I O N 78

A M I D E S FROM ALCOHOLS

S e c t i o n 78 Amides from A l c o h o l s

175

4-H 0

CH20H 1) HCrO, Ph

NHCOOMe

+

2 , I4e3SiI

Ph

Me

85%

Me

JOC, -46, 1616 (1931)

Phthwcti3 DEAD

Ph t h

w

Ph3P

NHTol Phth = p h t h a l i m i d o

JOC, 46, 1229 (1981) c

Roc

BI oc

OH

HN

Ph3P NHOBz

79%

DEAD

OBz JACS,

102, 7026

(1980)

176

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS V O L 5

SECTION 79

S e c t i o n 79 Amides f r o m Aldehydes

1) Me3SiCN P h - : a C H O

*

32)) LDA Ph2P0,NMe2

Ph-!@!-14Ve2

51%

4 ) H3@

phon

T e t r L e t t , 23, 3255 ( 1 9 8 2 ) c

0 II

0 II

PhO-CH2-C-0-P( OCH2CC1 3 )

P h- CH=NP h

Et3N

*

59%

0

Ph

S y n t h e s i s , 1053 ( 1 9 8 2 )

N-CH-COOMe

Y

1) TiC14

I1

COOMe

Bu

2) Me2C=C,

0

OMe

*

77%

OTMS

90% ee

3 ) LDA

-

T e t r L e t t , 21, 2077 and 2031 ( 1 9 8 0 ) S y n t h e s i s , 545 (1901)

SECTION 81

AMIDES FRON AMINES

177

S e c t i o n 80 Amides from A l k y l s , Methylenes and Aryls

No a d d i t i o n a l examples

S e c t i o n 81 Amides from Amides Conjugate r e d u c t i o n s o f u n s a t u r a t e d amides a r e l i s t e d i n S e c t i o n 74 ( A l k y l s from O l e f i n s ) .

0

0

2 BuBr

I1

Ph-C-NH2

ii

NaOH, P.T.C.

* Ph-C-N,

,Bu

9 3%

Bu

S y n t h e s i s , 1005 (1981)

H

Bz

Chem L e t t , 1143 (1981)

0 I1

n-C8HI7CNHCH3

1) N204, NaOAc 2,

0 I1

( ~ N H ~

T e t r L e t t , -23, 1127 (1982)

92%

178

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS V O L 5

SECTION 81

!n

C15H31-C-N

0

+

ci"

* 99% T e t r L e t t , _2 , 8 1 (1920)

KOH, benzene

0 11

Me 3C - CH- C - NH CMe I Br

13-crown-6 Synthesis , 586 ( 1982)

Boc

Boc

HO .CH3

HN

Ph3P NHOBz

*

0d - N \

DEAD

JACS,

w

102,

7026 (1980)

CH3 79%

OBz

S E C T I O N 81

A M I D E S FROM

AMIDES

Tetrahedron,

0 II

Me C H - CN H N H P h

36, 1311

(1980)

0

H2 ( 5 0 p s i )

I1

+ Me2CHC-NH2

Pd/C EtOH/HOAc

0

179

S y n t h Comrn,

0 II

100%

10

'

H

C-NH2

253 (1980)

0

II NC- OCH - 3

e l ec t r o 1y s is

71%

CH 30H Chem L e t t , 5 6 5 (1982)

0 II

H3C-C-N( CHO)?

I

H

75% CHO

S y n t h e s i s , 264 (1982)

180

COMPENDIUM OF ORGANIC SYNTHETIC FlETHODS VOL 5

1) 120°

+

+ 0 I1

*

Me2N-C(OMe)2 I

Me

2 , H20

S E C T I O N 81

0 I1

C - NH - C- Me

89 %

N02

S y n t h e s i s , 119 (1980)

S II

Bz-N-C-Me I

H

0

1) CSC12

I1

+

2 ) H20

75,':

Bz-N-C-Me I

H I n d i a n J Chem, 19B, 2 1 1 (1980)

S e c t i o n 82 h i d e s from Amines

0

OAc

S y n t h Comm,

95%

12,709

(1932)

AMIDES FR3M AMINES

S E C T I O N 82

181

0)0

S-t-CH3

*

t

0 11

CH 3- C- lit 1Ph

9 8%

Ph-NH2 S y n t h e s i s , 9 9 1 (19G1)

P h - 0- CH 2COOH

h-

t

*

Ph-0-CH

2

92%

S y n t h e s i s , 547 ( 19%)

GH

Me0

A"

OEt

-

CN.e,t

J O C , -45, 4519 (1980)

77%

182

COP4PENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 82

c1 MeS-t H-COC1

1) SnC14

CH2NHMe

2 ) Raney-Ni ethanol S y n t h e s i s , 534 ( 1 9 8 1 )

d”

CPFe(C0)2

1) Bu3P, C ; i 3 C N

20%

2 ) Ag20, THF CH3 JOC, -45, 1984 ( 1 9 8 0 )

0

-

11

c

+

0 ”

u

R e l a t e d methods:

3

1

-

1

H 1

N

1

( cti2 3

1

C

N

0

H

11

Chem L e t t , 159 ( 1 9 3 0 )

Amides f r o m C a r b o x y l i c A c i d s ( S e c t i o n 7 7 ) P r o t e c t i o n o f Amines ( S e c t i o n 105A)

1

89%

SECTION 83

A M I D E S FROM ESTERS

183

S e c t i o n 83 Amides from E s t e r s

-4

COOMe Me2A1NMe2

59,

Org Syn,

-n-C 17H 35 C O O E t

0 I1

C-NMe2

49 (1980)

e a

KOH, Bu4N HS04

9 3%

0 H C-NMe2 17 35 It

P

n-C

-

73%

Me2NH NO2 Chem L e t t , 285 (1981)

Ph,

CH:

0 ii

CH-C-OE t

1) LDA, THF

90%

2 ) PhCti=NPh JOC,

p h f i r h

0

45,

3413 (1980)

184

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS V O L 5

SECTION 84

S e c t i o n 84 Amides from Ethers and Epoxides

-

0

1) R C N , HBF4

2 ) NaOMe, MeOH

Tetr Lett, 2 2 , 341 (1981 1 c

S e c t i o n 85 Amides from Halides

I HNAc

CH3CN

I

JOC, 45, 165 (1980) I

CH2Br 0 JNHPh

KOH 94%

Bu4N 6 Br0

*

0& \ P h

Chem Pharm B u l l

, 29, 1063

(1981)

SECTION 86

A M I D E S FROM H Y D R I D E S

185

S e c t i o n 86 Amides f r o m H y d r i d e s

0

0 CH3-C-NHOH

-

PPA I1

OMe

6H3 59%

OMe

JOC, 46, 4304 ( 1 9 8 1 )

1) PhSeC1, CF,SO,H CH3CN 2 ) 30% H202

3

J

-

D N M c

J3C, 46, 4727 ( 1 9 3 1 ) 1

4 OTMS

n

t

78%

Tetr Lett,

1, 2033

(1980)

186

COMPENDIUM OF O R G A N I C SYNTidETIC METHODS VOL 5

SECTION 87

S e c t i o n 8 7 Amides from Ketones

0ll CH 3- C- P h

1) H2NOS03H, H20 2) a

0 I1

~60%

* CH3-C-NHPh

JOC (USSR) , jz,2234 ( 1 9 8 2 )

LYCHO0n2 H

4 1%

Helv C h i m A c t a ,

Me

$5, 2299

(1982)

Me S y n t h e s i s , 423 and 337 ( 1 9 3 0 )

AMIDES FROM NITRILES

S E C T I O N 88

187

S e c t i o n 88 Amides f r o m Ni t r i 1 es

Bu4N@HS04,a CH2C12 C-NH2

85%

H 2 O Z y H20, NaOH

S y n t h e s i s , 243 (1980)

Ph-CH2-CZN

KF _____t

a1 umi na

0 I1

74%

Ph-CH2-C-NH2

S y n t h Cornm,

12, 177

(1982)

39%

JOC,

47,

4812 (1932)

188

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 89

S e c t i o n 89 A m i d e s f r o m O l e f i n s

0 II

Hx,B

5

NaOH, P.T.C.

+

HX-NH-C-OEt

Synth Comm, 11, 475 (1981)

Ph-CH=CH2 t

1) H g ( NO3 ) 2 2 ) NaBH4

0 11

Me-C-NH-CH-CH3 1

Ph

CH 3-C-NH2 I1

0

JCS Chem Comm, 670 (1981)

2CS Chem Comm, 1173 (1981)

84%

SECTION 90

AMIDES FROM MISCELLANEOUS COMPOUNDS

''

189

Section 90 Amides from Miscellaneous Compounds -

0

OH

- b\H

TiC13, NaOH CH30H/H23

0

JOC, 45, 410 (1980)

Ce I V

'

72%

ZB'

Bz

(C0)5Cr=C, Me 'OMe

79%

JCS Chem Comrn, 297 (1980)

+

HT3-

OMe

r4e'$fs]

81%

0

JACS, __ 104, 5538 (1982)

Review: "Prominent Aspects o f Electroorganic Synthesis in lactam Chemistry."

B-

Bull SOC Chim Belges, 91, 951 (1982)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

190

SECTION 90A

Section 90A Protection o f Amides 0

0

604

CH20Bz

-

Synth Comm, 1 1 , 787 (1981)

A study o f N-acyl protecting groups for deoxynucleosides, including substituted phenyl acetyl , phenoxyacetyl , and benzoyl protecting groups.

-

Tetrahedron, 37 , 363 ( 1981 ) The N-acyl protecting groups in nucleoside derivatives can be selectively removed by treatment with ZnBr2 in the presence of alcohols to give 0-protected nucleosides.

-

Tetr Lett, 2 2 , 3761 (1981)

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 7 PREPARATION OF AMINES

S e c t i o n 91 Amines f r o m A c e t y l e n e s No a d d i t i o n a l examples S e c t i o n 92 Amines f r o m C a r b o x y l i c A c i d s and A c i d H a l i d e s No a d d i t i o n a l examples

S e c t i o n 93 Amines f r o m A l c o h o l s

Ph3P (OCH2CF3) t

2 ) BuNH2

n-C8H, 7NHBu

73%

n-C8H1 70H

JOC, 45, 5052 ( 1 9 8 0 )

Review:

" C a t a l y t i c A m i n a t i o n o f A l c o h o l s , Aldehydes, and Ketones" Russ Chem Rev, 49, 1 4 ( 1 9 8 0 )

192

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

N-OH

HN-CH,-i

S E C T I O N 93

-Bu 48%

-

D o k l a d y Chem, 244, 69 ( 1 9 7 9 )

S e c t i o n 94 Arnines f r o m Aldehydes

U

N

CH=NOH

NaBH4

2

TiC14

0

82%

S y n t h e s i s , 695 ( 1 9 8 0 )

Ph-CH=NPh

6

-i- P r O H Rh c a t a l y s t

*

Ph-CH2NH-Ph

85%

S y n t h e s i s , 442 ( 1 9 8 1 ) HN-CH2CH3 CH3-CHO 63%

H2, Cu/MgO

-

D o k l a d y Chern, 244, 69 ( 1 9 7 9 )

SECTION 94

AMINES FROM ALDEHYDES

NM

PhSeH

I1

193

HNI

w

P t1/ c \ H

w 83%

ph0cH2

PhCHO

n-C5H lCHO

t

PhCH2-N-Ph I

n-C5H11-CH2

PhSeH

PhNH2 T e t r L e t t , 21, 3385 (1980) c

p

1)

C-HO

Nil

NH

JACS,

"3

H-C-N

p NH2

94%

UIBAH

2)

%

HN

1) t - B u L i

2 ) PhCHO 3 ) MeOH, H20 4 ) KOH, HO , L

103, 4186

( 1981)

OuPh OH

JACS,

102, 7125

(1980)

5 7%

194

COMPENDIUM OF O R G A N I C SYNT;iETIC METHODS VOL 5

SECTION 94

n W CHo

Ph

a

'

,

NaH rn

fi@ 0 0 PBu3Br

JOC,

Review:

46,

3119 (1981)

" C a t a l y t i c A m i n a t i o n o f A l c o h o l s , A l d e h y d e s , and Ketones" 49, 14 (19ZO) Russ Chem Rev, -

R e l a t e d methods:

Amines f r o m Ketones ( S e c t i o n 102)

S e c t i o n 95 Amines f r o m A l k y l s , M e t h y l e n e s , and A r y l s No examples,

SECTION 96

AMINES FROM AMIDES

195

S e c t i o n 96 Amines from Amides

0

NaBH4

I1

n - Cg H 19 - C- NHBz

TiC14

n-C H CH NHBz * 919 2

9 3%

S y n t h e s i s , 695 ( 1980)

NaBH4 ,H'

DMSO

bw JOC,

46,

7 3%

2579 (1981)

CH2NH2 *HC1

I

1) BH3*SMe2

77%

2 ) e t h e r , HC1 S y n t h e s i s , 439 (1931)

Cti 3- C-Nt1P h

NaBH

1*

't

65%

+ CH3-CH2NHPh

JOC,

5, 3730

(1981)

196

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

S E C T I O N 96

0 II

C-NMe2

CH NMe2

BF3'0Et2 BH

9

7 G%

S Me2

TMEDA Synthesis

PhCH2-

99G (1981)

P h CH2- CH2-N

3 ) NaBH4

3

~70%

Tetr Lett,

R e l a t e d methods:

21, 4 0 6 1

(1930)

P r o t e c t i o n o f Amines ( S e c t i o n 105A)

S e c t i o n 9 7 Amines f r o m Amines NaEti4, H2C=0 PhNHEt

PhNH2

TH F NaBH4, H2C=0 THF

Me I

* Ph-N-Et

37%

-

98%

PhNMe2

Synthesis

743 (1930)

S E C T I O N 97

@

A M I N E S FROM A M I N E S

0

0

197

NHCH,

9 3%

COOE t

COOEt

3,3315

Tetr Lett,

Bz2Nt1

B u2 CuL i

*

(1982)

Bz2NBu

JOC,

62%

_42, 2739 (1980)

EtOH

H

74%

5% RhHL4

Et JCS Chem Comm, 6 1 1 ( 1 9 3 1 )

Ph-NH2

BuOti RuCl 2L3

*

79 %

PhNBu2

-

T e t r L e t t , 22, 2667 ( 1 9 8 1 )

198

H2N

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

n

RuCl 2L3 180'

NH2

0 N

SECTION 97

-0

90%

H

JOC, 46, 1759 (1981) L

1) 52 CUI 2 ) EtOCOCl

77%

3) PhMgBr

4)

s,

A

JOC,

47,

4315 (1982)

JOC, 45, 1515 (19CO) L

S E C T I O N 97

A M I N E S FROM A M I N E S

N=CHPh

199

NHMe

99%

N=CHPh

NHMe

S y n t h e s i s , 303 ( 1 9 G O ) 1) HC1, e t h e r

4 ) NaOti S y n t h e s i s , 5 4 1 (1981) NHMe

6 Me

@COOMe PdC12(CH3CN)?

*

0

JOC,

46,

2 5 6 1 (19E1)

COOMe

7 3%

200

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

m -

SECTION 97

CH31, 18-crown-6

t-BuOK,

37%

Et20

H

CH

JOC,

45,

3172 (1980)

Section 98 Amines from Esters No additional examples.

Section 99 Amines from Ethers

No addi t i onal examples

.

jection 100 Amines from Halides

1) Me2NNH2

60%

2 ) HN02

Br

NMe2

Synth Comm,

11,G O 1

(1982)

SECTION 100

AMINES FZGM HALIDES

201

Ph-N=PPh3

+ 2)

H20, O' H

*

Ph-NH

72%

I

Bu

BuI

Synthesis, 295 (1930)

Ph

Me - N H - CH 0

Ph

c

KOH

yJPh 90%

NHMe Synthesis , 39 (1930)

-n-C8H17-N3

NaBH4, H20 Toluene, P . T . C .

+

n-CoH 17-NH2

(from the ha1 i de) JOC,

47,4327

(1982)

( i s o l a t e d as the benzamide) JOC,

5,2822

(1982)

92%

202

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

SECTION 100

N

1) Ph Ph-Li

ACH2

2) H ~ O ,

P o r OH

68%

Ph-NH2

Many a r o r n a t i c and h e t e r o c y c l ic e x a m p l e s , Tetr Lett,

3,699

(1922)

COOMe

1) KNCO, ROH

Br

Br

2 ) Conc.

looo

HC1

Chem B e r ,

NH2

NH2

*Meo 114, 173

(1981)

DNH2 Cli $N

Meo
0

JOC, 46, 2991 (1961)

SECTION 100

AMINES FROM HALIDES

203

0

n-C8H17Br

94%

18-crown-6, to1 uene * @-‘aH17 0

Bull Chem SOC Japan,

H x - CH=C F2

LDA

E t20

-

55,

1671 (1932)

H x- C- C- N (iPr )

70%

p4e

Chem Lett, 935 (1980) Section 101 Amines f r o m Hydrides

0

Me2N=CH2 8

NMe2

79%

Tetr Lett, 21, 805 (1980) Me3N t

electrolysis

e

Me2NCH2CH ( COOEt )

H2C ( COOEt ) Tetrahedron, 37 , 2297 ( 1981 1

53%

204

COMPENDIUM OF O R G A N I C S Y N T i i E T I C METHODS V O L 5

SECTION 102

S e c t i o n 102 Amines f r o m Ketones

0 +

00

0

Bu4N BH3CN

H

94%

HC 1

46, 3571 ( 1 9 8 1 ) JOC, -

NOH

NaBH4 TiC14

-

91 %

S y n t h e s i s , 695 ( 1 9 8 0 )

0 R =

Bz, C-HX

-0 NHR

I

Na2S204 DElF

40-55%

32, 201 ( 1 9 7 9 ) A u s t J Chem, -

SECTION 102

AMINES FROM KETONES

205

Tetr L e t t , 22, 3447 (1981) OH

HN-CH - i - B u 2 -

i-Bu-CH20H H2, Cu/MgO

-0

48%

Doklady Chem, __ 244, 69 (1979)

244, 69 (1979) Doklady Chern, -

N II

x

H-C-NMe2

1) t-BuLi 2 ) -0

3 ) MeOH, H20 4 ) KOH, H20

102, 7125 (1980) JACS, -

206

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

S E C T I O N 102

% @

1) 2) DIBAH

-b2 98%

JACS, __ 103, 4186 ( 1 9 8 1 )

1 ) BuLi,

CH3-N,

2 ) NaBH4,

, CH2TMS CH=N-t-Bu -

66%

@ JACS, __ 104, 877 ( 1 9 8 2 )

Ph

QPh

Ph

electroreduction e t h a n o l , H2S04

a

P

h

H

Tetr Lett, 22, 3961 (1981 1

100%

S E C T I O N 102

Ph

A M I N E S FROM KETONES

207

0 I1

X

MeNHCHO +

c-Bu

MSC 1 L3

d

h

B

u

68%

I

Me JCS P e r k i n I , 700 (1981)

Me0

WMe CH2C1

OMe

70%

7 1 % ee Tetr Lett, 22, 3869 (1981)

208

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

/c\

\

.....

S E C T I O N 102

....A^..--

68% 96% ee Chem L e t t , 1765 and 1769 ( 1 9 8 2 )

Review:

" C a t a l y t i c A m i n a t i o n o f A l c o h o l s , Aldehydes, and K e t o n e s " Russ Chem Rev, 49, 14 ( 1 9 8 0 )

Review:

"The F r i e d 1 ander S y n t h e s i s o f Q u ino1 in e s " Org React, 28, 37 ( 1 9 8 2 )

R e l a t e d methods:

S e c t i o n 103 Amines f r o m N i t r i l e s 1 ) Me2S*BH3

/\/\/ C N

--

Amines f r o m Aldehydes ( S e c t i o n 9 4 )

2 ) HC1, H20 3 ) NaOH

NH2

72%

S y n t h e s i s , 605 ( 1 9 8 1 )

SECTION 104

AMINES FROM OLEFINS

209

H8N Bu

1 ) 2 BuLi 2) H20

Bu

92%

3) AcOH, H20

Synthesis, 270 (1981) Section 104 Amines f r o m Olefins

CB

1 ) BH3.THF 2 ) 5NH40H NaOCl

*

&'

5NH2

66%

JCS Chem Comm, 62 (1982) JOC, 46, 4296 (1981)

0

0 I,

( Et0l2P-NH2

ONH2 76%

1) H s ( N O ~ ) ~ ,CH3CHC12 2 ) NaBH4, NaOH/H20 3) H C 1 , benzene

Synthesis, 918 (1982)

210

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 104

1 ) [CpCo(N0)I2,

2 ) LiA1H4

70%

JACS, ___ 102, 5676 (1980)

-

Hg0.2HBF4

PhNH2, H20

Synthesis, 376 (1981)

Tetr Lett, 21, 809 (1980)

80%

SECTION 104

AMINES FROM OLEFINS

21 1

I

OMe

OMe Tetrahedron, 3 7 , 2895 ( 1981 1

TsONH2 90% CH2C1

JCS Chem Comm, 560 ( 1 9 8 0 )

NH

H Tetrahedron, 3 6 , 73 ( 1 9 8 0 )

212

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 104

74% S y n t h e s i s , 650 ( 1 9 8 0 )

S e c t i o n 105 Amines f r o m M i s c e l l a n e o u s Compounds

NaBH4, H20/Toluene C8H1 7-N3

C1 6 H 3 3 B ~ 3 @ B r o

*

C8H17-NH2

JOC, 47, 4327 ( 1 9 8 2 )

#

0

6

JOC, 46, 2593 (1981

Chem L e t t , 459 ( 1 9 8 0 )

92%

SECTION 105

AMINES FROM MISCELLANEOUS COMPOUNDS

NO

21 3

H

TiC14, NaBH4

87%

Synthesis, 741 (1980) Ph-N02

NaBH4-SnC1

EtOH

+

Ph-NH2 Chem Pharm Bull, 29, 1443 (1981)

VH2

N02

95% I

CH3

CH3

Chem Pharm Bull, 29, 1159 (1981)

H2NNH2 OPh

Raney Ni

96%

OPh Tetr Lett, 23, 147 (1982)

214

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 105

0 I1

NaO-C-H, KH2P04 Me

G

Me

81%

Me

O

Synth Comm, 1 1 , 925 (1981)

CH,

NH2

N02

JOC, 45, 4992 (1980) L i -NH3

94%

MeOH Synth Comm, 12, 293 (1982)

Ph-N02

A12Te3, H20

Ph-NH2

90%

Angew Chem Int Ed, 19, 1008 and 1010 (1980)

SECTION 105

AMINES FROM MISCELLANEOUS COMPOUNDS COPh

COPh

@

Fe3(C0Il2 A1 203,hexane

N02

Review:

68%

NH2

JCS Chem Comm, 821 (1980)

6 N02

-Q

215

-6

Chem Pharm Bull, 28, 2515 (1980) COY R U ~ ( C O ) ~ ~

100%

NaOH, H20/benzene P.T.C.

NH2

Tetr Lett, 21, 2603 (1980)

"Dihydropyridine Equivalents as Intermediates for the

Synthesis o f Alkaloids"

91, 985 (1982) Bull SOC Chim Belges, -

216

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

S E C T I O N 105A

S e c t i o n 105A P r o t e c t i o n o f Amines R e l a t e d methods:

Amides from Amines ( S e c t i o n 8 2 ) ; Amines Amides ( S e c t i o n 9 6 )

from

10, 469 ( 1 9 8 0 ) S y n t h Comm, -

0

C1 -C-OMe

I1

R-NH-C-OMe

R-NH2

MeS03H Chem L e t t , 705 ( 1 9 8 0 )

S E C T I O N 105A

0 II

R-N-C-OBZ I

H

PROTECTIOF; OF A M I N E S

H2,

Pd, E t 3 N

Me2NAc

NH3(l 1

*

R-NH2

21 7

~80%

R may c o n t a i n a w i d e v a r e t y o f o t h e r f u n c t i o n a l and p r o t e c t i n g

groups. Org Syn, 59, 159 ( 1 9 8 0 )

0 I1

R-N-C-OBZ I

H

0

NH4, HCOO' b

10% Pd/C

RNH2

S y n t h e s i s , 929 ( 1 9 8 0 )

ococ 1

@+O E t

Tetr Lett, 22, 3719 ( 1 9 8 1 )

>go%

218

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

k t

*

R-NH2

SECTION 105A

0 I,

R-N-C-OCMe3

%80-95%

1

H Tetr Lett, 21, 3065 ( 1 9 8 0 )

R' = t-Bu,

Bz, -CH2CH2TMS

JOC, 47, 2697 ( 1 9 8 2 )

0

0

(R-NHjC-0

Pr-NH2 o r H2NNH2

(TCroc

-

R-NH2

cF3

Used as an a m i n e - p r o t e c t i n g g r o u p i n p e p t i d e s y n t h e s i s .

JOC, 46, 4971 ( 1 9 8 1 )

SECTION 105A

PROTECTIOh OF AMINES

219

Ar=-CH2 OCH3

Tetr Lett, 23, 3843 (1982)

R-N-TS R' I

K,

crown ether diglyme

R-NH R' I

Chem Pharm Bull, 30, 3178 (1982)

JOC, 45, 547 (1980)

220

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 105A

Use o f v a r i o u s mu1 t i s u b s t i t u t e d b c n z e n e s u l f o n y l p r o t e c t i n g g r o u p s f o r the guanidino function o f arginine.

Removed b y T F A - t h i o a n i s o l e .

Chem Pharm B u l l , _2&’

2325 ( i 9 G i )

OMe

m I

H

Meo J SO,

OMe

HF o r CH3S03H

OMe

Used f o r t r y p t o p h a n i n p e p t i d e s y n t h e s i s . Chem Pharm B u l l ,

2,2825

(1932)

SECTION 105A

PROTECTION OF A M I N E S

221

1) ( j - P r ) 2 N E t

f-\ 2 ) CH2=CHCH2Br

R-NH2

R-N( CH2CH=CH2)2

CH3CN/H20 Tetr Lett,

Q

0 ii

H 3N - As n - C- OTMS

1) E t 3 N 2 ) Ph3CC1

2,1433

(19Gl)

H1

+ Ph3C-N-Asn-COOH

3 ) MeOH

75%

JOC, 47, 1324 ( 1 9 8 2 ) c

The DPPM g r o u p i s used t o p r o t e c t h i s t i d i n e i n p e p t i d e s y n t h e s i s , I t i s s t a b l e t o a c i d , b u t c l e a v e d b y Zn/HOAc o r e l e c t r o l y t i c r e d u c -

tion. N D C P h 2 -

= DPPM

JCS P e r k i n

0

R-NMe3

1-

L-Selectride +

R-NMe2

I, 522 ( 1 9 3 1 )

..80-90%

Org Prep Proc I n t , 12, 345 ( 1 9 8 0 )

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

222

SECTION 105A

0 I,

Me3C-C-OCH2C1

Me3CCOCH2 I

H I

JOC, 45, 1711 (13GO) c

Use o f t h e E - p h e n y l a c e t y l p r o t e c t i n g g r o u p f o r l y s i n e i n p e p t i d e synthesis.

D e p r o t e c t e d by a p e n i c i l l i n a r n i n o h y d r o l a s e enzyme. C o l l Czech Chem Cornm,

46,

1983 (1931)

Ph,C=NH

R2

I 3 1 C-C02R

n-

I

i /

NH~-HCI

R2

3

I

R1- C-CO,R I

N HC1, E t 2 0

JOC,

L

NkCPh2

47,

2663 (1382)

SECTION 1 0 5 A

+

223

PROTECTION OF AMINES

bh

anodic oxidation CH2C1 2 / E t 4 N B F 4

T Y H R-i)QoPh

R-NH2

CH2C12 U s e d f o r amino a c i d e s t e r s . A n g e w Chem I n t Ed, 19, 712 ( 1 9 8 0 )

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 8 PREPARATION OF ESTERS S e c t on 106 E s t e r s f r o m A c e t y l e n e s

-B' w f

I

r- ri I

C O Y PdC12, SnC12

L=L'l

PBu3, CH3CN JACS,

P h - Cz C-P h

m o -n

-lE7520 ,

(1981)

C O Y Rh c a t a l y s t

t

MeOH

33%

Ph

NaOAc

'OMe Chem L e t t , 993 ( 1 9 8 1 )

Et

* PdC12, NaOAc

y

Et

C O Y MeOH

Chem L e t t , 879 ( 1 9 3 1 )

Et

COOMe

95%

S E C T I O N 107

ESTERS FROM CARBOXYLIC A C I D S , A C I D HALIDES,

225

AND ANHYDRIDES S e c t i o n 107 E s t e r s f r o m C a r b o x y l i c A c i d s , A c i d H a l i d e s , and Anhydrides

The f o l l o w i n g t y p e s o f r e a c t i o n s a r e f o u n d i n t h i s s e c t i o n : 1.

Esters from t h e r e a c t i o n o f a l c o h o l s w i t h c a r b o x y l i c acids, a c i d h a l i d e s , and anhydrides,

2.

Lactones from hydroxy acids.

3.

E s t e r s f r o m c a r b o x y l i c a c i d s and h a l i d e s , s u l f o x i d e s , and m i s c e l l a n e o u s compounds.

R-COOH t

R'-OH

0

DCC

w

polymer-bound

I1

R-C-OR'

NMe2

B u l l Chem SOC Japan,

*

NPS- NH- CH- COOH I

CH2Ph

DCC

BzOli

3, 6 3 1

0 I1 NPS-NH- CH- C-OBz

* I

CH2Ph

No r a c e m i z a t i o n .

JCS Chem Comm, 1132 ( 1 3 3 2 )

(1981)

92%

226

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS V O L 5

Z-Pro-COOH

t-BuOH, c a r b o d i i m i d e +

DMAP, CH2C12

SECTION 107

Z-Pro-COO-t-Bu -

88%

No racerni za t i on. JOC, 47, 1962 ( 1 9 8 2 ) c

1) S02C1F, E t 3 N P h- COOH

2 ) BzOH, E t 3 N

0 I1

Ph-C-OBz

GO%

S y n t h e s i s , 790 ( 1981)

1) CH3S02C1, E t 3 N

S y n t h Comrn,

12, 727

(1982)

1) C1S02NC0,

C 11H2 3COOH

Et3N

2) EtOH

*

CllH23COOEt

S y n t h e s i s , 506 ( 1 9 8 2 )

80%

SECTION 1 0 7

ESTERS FROM CARBOXYLIC ACIDS, A C I D HALIDES,

227

AND ANHYDRIDES

0

S y n t h Cornm,

Pr-COOH

6I - "14

o\-

c1

t

Et3N

Bu-Otl

-

_12, 6 C 1

(1922)

0 11

90%

Pr-C-OBu

S y n t h e s i s , 547 (1980)

1) B u 3 P 1 2 0

E t 2 0 , HMPT

7 3%

+OOH 2)

--)-OH A u s t J Chem,

22,

517 ( 1 9 3 2 )

-6

COOMe

M e 3 S i CHN2 MeOH

Chem P h a r m B u l l ,

100%

29,

1475 (1931)

228

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 1 0 7

0 11

@

1) TMS-CHN2 2 ) BzOH, E t 3 N Chem P h a r m B u l l T e t r Lett,

,

2 9 , 3 2 4 9 (1981)

c

3,44G1

(1930)

+

95%

c1 N02 B u l l Chem SOC J a p a n ,

P h 2CH COOH

54,

1470 ( 1 9 8 1 )

0

02N+No2 NO2

11

t

+

Ph,CHC-OCH,CH=CHPh 1

1

PhCH=CHCH20ti

99% S y n t h Comm,

11,121 (19C1)

SECTION 107

ESTERS FROM CARBOXYLIC ACIDS, ACID HALIDES, AND ANHYDRIDES

n-C5H lCOOH t

CD

c1,

C=NMe2 Me2N , pyridine

0 I1

w

t-BuOH

~-C5Hll-C-O-t-Bu -

229

77%

Chem Lett, 1891 (1982)

Ph( CH2) 3COOH t

rt

942

CSF Chem Lett, 391 (1980)

86':?

O2

COOH

w Ph

0

BzOH, Et3N

b

0 11

Ph

&-OBz

Chem Lett, 1161 (1980)

92%

230

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

0

SECTION 1 0 7

0 i1

Me 3C - C 0 0t i

Me3C-C-OBz

79%

2 ) BzOH Chem P h a r m B u l l

L

2 ) L-BuOH,

(1982)

0 P h - CH C H C tl C - 0 - t - B u 7 5%

L

Ph-CH2CH2CH,COOH

, 3,2 6 3 3

DBU Synthesis, 833 (1932)

0 I1

0

CH 30H

I1

n-C ti C-0-C-CF3 - 17 35

i

n-C

-

0 ,I

9 1%

H C-OMe 17 35

C a n J Chem,

2, 2 6 1 7

(1981)

/

A

HO ( CH2) 14COOH

Bu2Sn0

c=o

6 d

(ct'2)14

JACS, 1 0 2 , 7 5 7 3 (1980)

63%

SECTION 107

ESTERS

FROM

CARBOXYLIC ACIDS, ACID HALIDES, AND ANHYDRIDES

231

Ph

H

(CH2)15

e

90% ,,111111111111111111lllllllllll=O

COOH

Angew Chem Int Ed, 20, 771 ( 1 9 8 1 )

X0 0

~

E t 3 N , acetone H

Tetr Lett, 21, 1893 (1980)

6

-4

0

86%

COOEt

EtBr

DBU, Cti3CN

Org Prep Proc Int, Jl, 225 (19GOj

96%

232

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

SECTION 107

0 C-OMe I1

(MeO)2S0 C O COOH O H

79%

C-OMe 0

H2S04

Indian J Chem, 2lJ,

Q

00 C-C-OH II

00 C-C-OEt I1

I1

+@

C1 COOEt Et3N

NHAc

Tetr.Lett,

0 II ( Et0)2P-CC1

I1

2.93% NHAc

zLy 4997

Synth Comm, COOH I

259 (1982)

12,453

(1930)

(1982)

COOEt 1

93%

Tetrahedron, 38, 1457 ( 1982)

SECTION 108

Review:

ESTERS FROM ALCOHOLS AND PHENOLS

233

"Recent Developments i n Methods f o r t h e E s t e r i f i c a t i o n a n d P r o t e c t i o n o f t h e Carboxyl Group"

36, 2405

Tetrahedron,

F u r t h e r examples of t h e r e a c t i o n RCOOH + f?OH

+

(1930)

RCOOR a r e included

i n S e c t i o n 108 ( E s t e r s from Alcohols and Phenols) a n d S e c t i o n 10A ( P r o t e c t i o n o f Carboxyl i c A c i d s ) . S e c t i o n 108 E s t e r s from Alcohols and Phenols OH

EtOAc L

n e u t r a l a1 umina

OAc S y n t h e s i s , 785 (1581) T e t r L e t t , 2, 5003 and 5007 (1981)

00 II

n-C3H170H

I1

Ph-C-P(OEt)2 DBL', CtI,Cl,

0

I1

* E-C8Hl7-0-C-Ph

-

T e t r L e t t , 2 2 , 3617 (1931)

234

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

Q

SECTION 108

CH20Ac

@

CH20H

Ac20

+

BF3*Et20

OH

68%

OH

a

Chem Pharm Bull ,

OH

AcO

0 0

L

9, 3202 O

(1981)

A

c 61%

Cs F

Chem Lett, 563 (1981)

Bull Chem S O C Japan,

24, 1267

(1931)

82% U

Synthesis, 991 (1981)

SECTION 108

235

ESTERS FROM ALCOHOLS AND PHENOLS

HCOOH

OH

90%

0- C-H

BF3.2 MeOH

II

0 Org Prep Proc I n t ,

2,177

(1982)

‘2cHph

Ph-C-N ”

t

CH 3 CH3

S y n t h e s i s , 485 ( 1 9 8 0 )

n

Ph

99%

S y n t h Comm,

H

1111

VHC 3

(1980)

VH 3

1) MeS02C1 E t 3 N 2 ) EtC02Cs, DMF

8G%

EtCO2llIl C

b

JOC,

2,831

46,

HC“ 4 3 2 1 (1931)

5 H 11

236

B

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

u

-

p

OH

S E C T I O N 108

n

Br2

BU-(.~>O

NifO-C-pentyl] I1

70%

0

OH

-

JOC, 46, 4206 (1931)

OH

Rut i

L4

Go

*

96%

acetone

T e t r L e t t , 22, 5327 ( 1 9 8 1 )

mo c

CH20H

CH~OH

IiLADH enzyme +

NAD+

v

-

79% 100% ee

JCS Chem Comm, 515 ( 1 9 8 0 ) JACS,

104,4659

(1982)

1) T1 (OCOCF,)

CF3COOH

WII

2 ) PdCl,,

co

L

LiCl

,

MgO

JACS, 104, 1900 ( 1 9 8 2 ) F u r t h e r examples of t h e r e a c t i o n ROH + R ' C O O R a r e i n c l u d e d i n S e c t i o n 107 ( E s t e r s f r o m C a r b o x y l i c A c i d s and A c i d H a l i d e s ) and S e c t i o n 45A ( P r o t e c t i o n o f A l c o h o l s and P h e n o l s ) .

SECTION 109

ESTERS FROM ALDEHYDES

237

S e c t i o n 109 E s t e r s from Aldehydes

0 I1

NaOCl

C-OMe 53%

HOAc, MeOH

Tetr L e t t , 23, 4647 (19C2)

1) t-BUOC1

GO%

2 ) E t 3 N , MeOti

6

JOC,

1360 (1932)

0 It C - OMe e l e c trochemi ca 1 o x i d a t i o n

83%

Cti30H, NaCN, P t anode

Me

Me

Meom

B u l l Chem SOC Japan, -55, 335 (1982)

laCH0 MCPBA

Meo

47,

KF

O-C-H

Me0

Tetr L e t t , 22, 3895 (1931)

'd

90%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

238

- 4’

ACOOMe t

CH3( Cti2)4CH0

SECTION 109

86%

+e-, Me3SiC1 DMF-Et4NOTS

21, 5029 ( 1 9 8 0 ) Tetr Lett, -

1) NaH, DMF

- mo 92%

2 ) Me3Si-CH=C=O

S y n t h e s i s , 672 ( 1 9 8 2 )

1) TMSCN, KCN CH3

18-crown-6

~70%

2) p y r i d i n i u m dichromate CHO

DMF

0 Tetr Lett, 21, 731 (1980)

1) E t 2 0 , 15-20 k b a r ‘ g H l l

0

2 ) Moo3, 30% H202 3 ) Ac20, p y r i d i n e

5 3%

OMe

JOC,

5,2230

(1981)

SECTION 1 1 1

ESTERS FROM AMIDES

OS02Me

Ni ( C O ) 4

239

*

benzene

JACS, 103, 3945 (1981) Related methods:

E s t e r s from Ketones ( S e c t i o n 117)

S e c t i o n 110 E s t e r s from A1 kyls , Methyl enes and Aryl s

No examples o f t h e r e a c t i o n R R

-f

RCOOR' o r R ' C O O R ( R , R ' = a1 kyl ,

a r y l , e t c . ) occur in the l i t e r a t u r e .

For t h e r e a c t i o n RH

-f

RCOOR'

o r R'COOR s e e S e c t i o n 116 ( E s t e r s from H y d r i d e s ) . S e c t i o n 111 E s t e r s from Amides

0I ' CH3( C H 2 ) 6-CNHNH2

cut+

CH3(CH2)6-C-0 0 # Tetrahedron, 36, 1311 (1980)

77%

240

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

d

S E C T I O N 111

OH

CH30H

C-OCH3

C-NH2 II

63%

JOC, 46, 5 3 5 1 ( 1 9 8 1 ) c

S e c t i o n 112 E s t e r s f r o m Amines No a d d i t i o n a l examples.

S e c t i o n 113 E s t e r s f r o m E s t e r s C o n j u g a t e r e d u c t i o n s a n d c o n j u g a t e a1 k y l a t i o n s o f u n s a t u r a t e d e s t e r s a r e f o u n d i n S e c t i o n 74 ( A l k y l s f r o m O l e f i n s ) .

0 I1

PhCH2-C-OEt

0

T i (OEt)4

I1

P

BzOH

PhCH2-C-OBZ

85%

S y n t h e s i s , 138 ( 1 9 8 2 )

+o

C-OMe

1) 12, M e 3 S i I 2 ) Me2CtiOti

C-OCHMe2

S y n t h e s i s , 142 (19G1)

7 1%

S E C T I O N 113

ESTERS FROM ESTERS

241

0 I1

OH

C-0-t-BU -2e

30%

t-BuOH

-

Tetr L e t t , 2 2 , 3715 (1981)

-

( PhSe0)20 Ph-C-0

; Ph-C-0

x}

69%

JCS Perkin I , 1650 (1930)

JCS Cheni Cornrn, 1231 (1931)

S-t-Bu -

t-EuOH -CH3CN

-dj

Org Syn,

- t-- B U

61,

48 (1983)

90%

242

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

Pb( OAC ) 3

*

SECTION 113

COOEt

9 1%

Aust J Chem, 33, 113 (1980)

1)

f CH2MgBr LCH2Mg6r

80%

2) t$O Tetr Lett,

2, 4167

(1930)

1) GrMg(CH2)4MgBr

54%

2) Jones

JOC,

45,

1828 (1980)

Tetr Lett,

z,5189 (1982)

SECTION 114

ESTERS FROM ETHERS AND EPOXIDES

243

JACS, 104, 5 5 4 3 ( 1 9 3 2 ) I _

Syntti Comm, 0 I1

,C-Ph

HN\CH( COOEt)2

1) Brz

11,35

(1981)

0

2) H h i g ' s base 3) BuLi 4 ) H30Q

I1

* HN,

,C-Ph

66%

CI ( C O O E t ) , Bu

Angew Chem I n t Ed,

21, 2 0 3

(1932)

S e c t i o n 114 Esters f r o m Ethers a n d E p o x i d e s

1) S02C12, p y r i d i n e

C3H 17-CH2SPh

w

2 ) MeOH/H20

0 11 C8ti17-C-OMe

JCS Chem Comm, 8 5 7 ( 1 9 8 2 )

76%

244

COMPENDIUM OF ORGANIC S Y N T H E T I C METHODS VOL 5

1i3P05, 0

0

S E C T I O N 114

0 44%

CH3CN JOC, 45, 1320 (1980)

R u0 / P ia I O4

59%

cc1 4/1i,o

L

S y n t t i Conirn,

t-BuCOC1

I

NaI

lo, 2 0 5

(1930)

4% 84%

C -t-Bu

0

T e t r L e t t , -23, 681 (1932)

PhCH2PdC1 ( P P h 3 ) 2 w

Bu3SnC1, Ph-C-C1

dH

I1

0 J3C,

47, 1 2 1 5

2 1% (1932)

SECTION 115

4

ESTERS FROM HALIDES

Tetr Lett,

coo%aQ

P b ( OA c )

-

245

22,

5191 (1981)

&o 100%

OMe

OMe Chem L e t t , 879 ( 1 9 8 2 )

S e c t i o n 115 E s t e r s from H a l i d e s

MeSCH2S0,Me n-C 12H 25 B r -

,

t c l uene w

L

50% NaOH, P.T.C.

SM ,e n-C12H25-CH

-

.I.

\

S02Me

-n-C 12H 25 CO 2Me Tetr Lett, 22, 4499 (1981)

83%

246

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5 silica gel

C02E t

xyl ene

Br

-7)

SECTION 1 1 5

+

79% 0

Chem Lett, 1909 (1982)

co

71%

PdL2C12, THF JACS, _1l, 4193 (1980)

YBr

PdL4, CO

93%

MeCN, K2C03, 70' JOC,

47,3630

(1982)

SECTION 116

ESTERS FROM HYDRIDES

Ni ( C O ) 4

Et3N

247

JOC,

96%

5, 1723

(1981)

Carboxylic Acids from H a l i d e s ( S e c t i o n 25)

Related methods:

S e c t i o n 116 E s t e r s from Hydrides This s e c t i o n c o n t a i n s examples of t h e r e a c t i o n RH R'COOR ( R

=

+

RCOOR' o r

a l k y l , aryl , e t c . ) .

0 I1 C-OMe

1) T1 ( T F A ) 3 80%

2 ) C O Y MeOH PdC12, LiCl/MgO JACS,

JOC,

0

0 I1

MeSCH2COOEt P

TsOH

2, 1900

45,

(1982)

363 (1980)

SMe I Ph-CH-COOEt

T e t r L e t t , -2 2 , 31 (1931)

88%

248

COMPENDIUM

OF ORGANIC S Y N T H E T I C METHODS VOL 5

SECTION 1 1 6

77%

N a O A c , AcOH I

OMe

OMe

S y n t h e s i s , 477 (1930)

0

C

CH2COOE t

II

EtOC-CH2N2

90% J C S C h e m Comm, 688 (1981)

PdC12, CuC12

-

COOMe

6 3%

-

PPh3, NaOAc, HOAc

Angew Chem I n t E d , 21, 366 ( 1 9 C 2 ) P d C 1 2 , KOAc C5H110N0

*

Yco 52%

OAc

T e t r Lett, 22, 131 (1981)

ESTERS FROM H Y D R I D E S

SECTION 116

249

co C5H l-C- CH

PdC12, C u C 1 2

NaOAc, MeOH

*

C H

Tetr Lett,

JOC,

6

1) AcCl

, Ac20,

74%

5 11-C-C-C02Me

46,

21, 849

(1930)

2 7 1 7 (1981)

pyridine

60%

2 ) H20, a

S y n t h e s i s , 223 (1981)

Tetr Lett,

21, 2557

(1980)

250

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

S E C T I O N 116

H3ca0 - H3c [q H {IC CF3COOH

l!!ph

0

F3CS03t I

/C-Ph

77%

S y n t h e s i s , 4G1 (1980)

-

1) TMSCN, KCN

18-crown-6

CHO

z

na70%

2) p y r i d i n i u m dichromate

0

DMF T e t r L e t t , 21, 7 3 1 (1330) L

1) NaH, DMSO E t-CH2N02

-

0 I1

Et-CH-C-OEt I

55-80%

N02 O=C-OEt Angew Chem I n t Ed, 21, 139 (1982) c

Fe++/

S O8 -

CH,CH,COOH 3

L

CH3CH2COONa

P 3c

h

d

:

95%

(33% convers i o n )

Tetrahedron,

36, 3559

(1980)

SECTION 117

Also v i a :

ESTERS FROM KETONES

251

C a r b o x y l i c a c i d s , S e c t i o n 2G; A l c o h o l s , S e c t i o n 41

S e c t i o n 117 E s t e r s f r o m Ketones

0 I1

Ph-C-CH3

0

1) BF3*OEt,L

I1

2) Pb(OAc)4, MeOH

w

Ph-CH2-C-OMe

86%

S y n t h e s i s , 126 (1981)

0

0 I1

C-CtI,CH,

CH3

Pb ( OAc )

-(i

S y n t h e s i s , 456 (1922)

49%

JOC,

5, 1914

(1981)

252

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 117

1) NaH, DME 2) Et3N, MeCN

Oti

II

N02 Tetr Lett, 23, 3521 (1982)

B

oh.;

0 %70%

COOMe

COOMe

Zn, CH3CN

66%

Cliem Lett, 1217 (1951)

y 3

0' 0 CH3 1) (Me2N)P-CH=b-CH 0 2 I1

I

2) HC1 , H20, CH30H

6

Synthesis, 289 (1980) OMe 1)

2) H20, HC1

OO

$'

Chem Lett, 1567 (1980)

2.50%

SECTION 118

253

ESTERS FROM NITRILES

iACS,

104,6879

(1932)

A l s o v i a C a r b o x y l i c A c i d s , S e c t i o n 27

S e c t i o n 118 E s t e r s f r o m N i t r i l e s

I) tic1 CH30H y

11

* Me-C-CH2COOEt

Me-CN 3 ) NaOEt Synthesis

130 ( 1 9 3 1 )

35%

254

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 119

S e c t i o n 119 Esters from O l e f i n s

-

Ph

Tetr Lett, 22, 1783 ( 1 9 8 1 ) JOC, 45, 695 and 1538 ( 1 9 8 0 ) c

+

Cu2Br2

wcooit 7 1%

COOE t

DMSO

Br2C(C O O E t ) 2

Ph

Bull Chem SOC J a p a n ,

3, 2539

(1981)

Pb(OAc)4 98%

CH3CN

Tetr L e t t , 0 I1

C2F5C-OC1

CF2=Cti 2

C1 F NaF

w

21,1819

0 I1 C2F5C-OCF2CH2C1 JOC, -45, 1214 ( 1 9 3 0 )

A l s o v i a A l c o h o l s , S e c t i o n 44

(1980)

80%

PROTECTION OF ESTERS

SECTION 120A

255

Section 120 Esters from Miscellaneous Compounds

No additional examples.

Section 120A Protection o f Esters

1) EtSH, A 1 C 1 3 2 ) AgN03, MeOti col 1 i di ne JOC, -45 - , 740 (1980)

76%

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 9 PREPARATION OF ETHERS AND EPOXIDES S e c t i o n 121 E t h e r s and Epoxides from Acetylenes No examples.

S e c t i o n 122 Epoxides from A c i d H a l i d e s

0

1) C1 CH=CHCH2TMS A1C13 2) NaBH4, MeOH

74%

3) NaOH Tetr Lett,

3, 4369

(1980)

S e c t i o n 123 E t h e r s and Epoxides from A l c o h o l s and Phenols

/OBU

C0

1) NaOH, H20

70% 2 ) BuCl

OH

OH JOC,

45,

1095 (1980)

SECTION 123

ETHERS AND E P O X I D E S FROM ALCOHOLS AND PHENOLS

MeI, KF-a1 umi na

C8H170Me

+

‘gH 170H

257

90% OMe

QH

I

Me1 , KF-a1 umina

782

B u l l Chem S O C Japan,

2, 2504

(1982)

t-BuC1 Ph-OH

N i (acac)2 t

NaHC03

322

Ph-O-t-Bu S y n t h e s i s , 186 ( 1 9 8 2 )

NH II

R-OH

BzOCCCl TfOH , hexane/CH2C1

t

:CS

Ar-OH

BzOTs t

82-98%

R-0-BZ

Chem Comm, 1240 ( 1 9 8 1 )

Ar-OBz S y n t h Comm,

11,053

(1981)

Me2S0, P h I

t-Bua 30% JOC, 47, 4374 ( 1 9 8 2 ) I

258

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 123

OPh Ph4BiOCOCF3

6

58% JCS Chem Comm, 503 (1981) OCH2CF3 I

CF3CH2CS02Me

86%

HMPT, n N02

N02

Synthesis, 727 (1980)

A

A1203

(;IH

Bull Chem

Naf i on-H

SOC Japan,

53,

3031 (1980)

w

CH20H

Synthesis, 474 (1981)

90%

SECTION 123

OH

ETHERS AND EPOXIDES FROM ALCOHOLS AND PHENOLS

3

SPh

JACS,

103, 7393

(1981)

JOC, 46, 3361 (1981) 1) B u L i , THF

Synthesis, 550 (1981)

259

260

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 123

PhI=O BF3*Et20 ‘6”13 &TNS

65% JCS Chem Cornrn, 1108 (19G2)

Ph3P DEAD

OH JCS Chem Comrn, 784 ( 1 9 8 0 ) R e l a t e d methods:

P r o t e c t i o n o f A l c o h o l s and Phenols ( S e c t i o n 45A)

S e c t i o n 124 Epoxides f r o m Aldehydes

Ph-CHO

Me3S8 I 0

KOH,

m o i s t CH3CN

w

Ph-CI

H

/O\

CH,

L

96%

T e t r L e t t , 23, 5283 ( 1 9 8 2 ) c

Ph-CHO

VH3 Ph-Se=CH2

* Ph

94%

20, 671 ( 1 9 8 1 ) Angew Chem I n t Ed, -

SECTION 128

ETHERS FROM ESTERS

26 1

G3 Ph3AsCH2CHMe2

n-C7H15-CH0

72% K N ( SiMe3)

C7H15 JACS, 103, 1283 (1931)

Related methods:

Ethers a n d Epoxides from Ketones (Section 132)

Section 125 Ethers a n d Epoxides from Alkyls, flethylenes a n d Aryls

No examples o f the preparation of ethers a n d epoxides by replacement of a l k y l , methylene, a n d aryl groups occur in the l i t e r a t u r e .

For the conversion of RH

+

R O R ' (R, R '

=

a l k y l ) see Section 131

(Ethers from Hydrides)

Section 126 Ethers a n d Epoxides from Amides

No additional examples.

Section 127 Ethers a n d Epoxides from Amines

No additional examples,

Section 128 Ethers from Esters

Ph-OAc

CH 3CH2CH2 I

K2C03, 18-crown-6

F

Ph-0-CH2CH2CH3

JCS Chem Comm, 815 (1982)

79%

262

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

Ph-C-0-i-Pr

Ph-CH2-O-i-Pr 2) R a - l i i

JOC,

fi

Ph

SECTION 128

!a,

69%

332 (1931)

1) DIBAL-H

2) Et3SiH BF3.0Et2

O

JOC, -46, 2417 (1981)

P

h

72%

SECTION 130

ETHERS FROM HALIDES

263

S e c t i o n 129 E t h e r s from Epoxides

Naf i on-H

74%

MeOH/ether

OMe S y n t h e s i s , 280 (1981)

S e c t i o n 130 E t h e r s from Halides

-

n- C8H 7B r

KOH

t

& M (e(O --7H C 8lE -

DMF J

Also can be used t c form diary1 e t h e r s . S y n t h e s i s , 823 ( 1932)

NaOH, H20 benzene, Bu41iC1 S y n t h e s i s , 921 (1980)

84% OPh

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

264

SECTION 130

-t-BuC1

N i ( acac)2

Ph-OH

NaHC03

Ph-O-i-Bu

w

32%

S y n t h e s i s , 186 ( 1 9 3 2 ) R e l a t e d methods:

E t h e r s f r o m A l c o h o l s ( S e c t i o n 123)

S e c t i o n 131 E t h e r s f r o m H y d r i d e s

Ph-CH2COOMe

1) P h I ( O A c ) 2 w

2 ) NaOMe, MeOH

P h- CHCOOMe

OMe

Tetr Lett,

H

70%

1

ZL, 2747

(1931)

CH3-OH 88% -2eS y n t h e s i s , 315 ( 1 9 8 0 )

OTI..lS

I

t

Ph-CH(OMe)*

-@

86%

Ph

TfOTMS

Tetr Lett,

JACS,

21, 2527

102, 3248

(92% e r y t h r o ) (1980)

(1980)

ETHERS AND EPOXIDES FROM KETONES

SECTION 132

265

S e c t i o n 132 hthers a n d E p o x i d e s from Ketones

Chem a n d I n d , 388 ( 1 9 8 0 )

JOC,

FH

289 (1981)

3 Ph-Se=CH2

0 Bu

56,

Bu

Et

Et

Angew Chem I n t Ed, 2 0 , 671 ( 1 9 8 1 )

JACS,

103, 1 2 3 3

(1931)

266

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 132

21, 4307 and 4211 (1920) T e t r L e t t , -Related methods:

Epoxides from Aldehydes ( S e c t i o n 124)

S e c t i o n 133 E t h e r s and Epoxides from N i t r i l e s No a d d i t i o n a l examples.

S e c t i o n 134 E t h e r s and Epoxides from O l e f i n s

Org Syn, 6 1 , 112 (1983) I

f OH

1) PhSeCl

, CH2C12 c

2 ) RaNi, H 2

0

JXS , 102, 3784 (1930)

90%

SECTION 134

ETHERS AND E P O X I D E S FROM OLEFINS

267

electrolysis JACS,

,&I

4606 (1981)

H202, CH3CN

61%

CH30W , KHC03 Org Syn, $3, 63 (1981)

H202 Y $0

80%

(C1 2CH) 2C=0 Na2HP04 Tetr Lett,

2,2089

(1981)

MCPBA

>95%

KF Tetr Lett,

2,3895

(1981)

268

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 134

02, hv

Ph-C-CH-Ph I 0 OH II

L

JACS, 103, 2049 (1981)

+ OAc

0

%

JACS , -104, 6450 (1982)

HSOF K@

70%

98%

18- crown- 6 JOC,

35,4753 (1980)

KHS05 , acetone

*

OHj?- (

18-crown-6, CH2C12/H20

JOC,

47,

6

2670 (1932)

0

91%

SECTION 1 3 4

ETHERS AND

t-BuOOH, V5+ -

---

HO

EPOXIDES FROM O L E F I N S

269

--- 4 HO

CH3 JACS,

103, 7690

CH 3

(1981)

(t-BuO) 3 A l

72%

t-BuOOH

Tetr Lett,

1) t-BuOOH

%OH

21,

1657 (1930)

, T i ( O-L-Pr)4

(+)-dimethyl t a r t r a t e

OH

2) H20, NaF

79% JACS,

jl, 5974

(1980)

95% ee

JACS, _1l, 464 ( 1 9 8 1 ) a - N 6 R 3 Bro I ,

H20, e l e c t r o l y s i s

73%

JOC,

2, 3575

(1982)

270

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

JOC,

Q

0 I1 ( Et0)2P-CN

47,1141

SECTION 134

(1982)

H202 25%

Chem Pharm Bull

MeOOC

electrolysis

MeOOC

MeCN/H20, NaBr

MeOOC

29,

1774 (1981)

wcl

MeOOC

JOC,

46,

97%

3312 (1981)

NaOCl

m

Bu4NBr

0

CH2C1

,-7

Gazz Chim Ital , 110,267 (1980)

SECTION 135

ETHERS AND EPOXIDES FROM MISCELLANEOUS COMPOUNDS

, -

271

Section 135 Ethers and Epoxides from Miscellaneous Compounds

D-mannitol

?,,CH20Ts

O X 0

1) BuLi, CuI

2) AcOH, HBr

t

3) ~-C5H110K,

"optical ly pure"

Angew Chem Int Ed, 19, 198 (1980)

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 10 PREPARATION OF HALIDES AND SULFONATES Section 136 Hal ides from Acetylenes Amberlys t A-26 ( perbromi de form) Bu-CzCH

e

94%

BU>C=CHBr Br

Synthesis, 143 (1930)

- xC1 Ph

Ph-C=C-Me

c1-

85%

Me

-

Bull Chem SOC Japan, 54, 2843 (1981)

1) ca techol borane HCsC- ( C H 2 ) 8COOE4e

2 ) H20 3) IC1, NaOAc

e

H ’I

‘C=CH(

CH2)8COOMe 70%

Synth Comm, 11, 247 (1931) I

Section 137 Halides from Carboxylic Acids

-t - B u O I , hv 58%

Freon 113 JOC,

2, 4226

(1980)

SECTION 138

HALIDES AND SULFONATES FROM ALCOHOLS

273

S e c t i o n 138 H a l i d e s and S u l f o n a t e s f r o m A l c o h o l s

2"

Me Pi@= CH C 1 P02C1

*

OH

LI

S y n t h e s i s , 746 ( 1 9 8 0 )

- &'

(C1 3c )2c=o &OH

*

OH

JOC, HBr *

LiBr

46,

824 ( 1 9 8 1 )

d

1) PhSeCN

2) Br2, Et3N HO

-

9

Br

B u l l Chem S O C Japan,

Bu3P

>go%

,\$'

Br

53, 1181

(1980

a1

JCS Chem Comm, 656 ( 1 9 8 0 )

274

COMPENDIUM

OH

OF O R G A N I C S Y N T H E T I C METHODS VOL 5

S E C T I O N 138

-0 Br I

M e 3 S i C 1 , LiBr

or HMDS,

PyH@Br?

92%

JOC, 45, 1638 (1930)

Ph3P12 w

HMPT A u s t J Chem,

ti-CcC-CH20H

Bu3P12 HMPT

*

32%

35,

5 1 7 (1932)

H-CzC-CIi21 A u s t J Chem,

60%

3,517

(1982)

885%

BnO

JCS P e r k i n I, 2866 (1980)

SECTION 140

HALIDES FROM ALKYLS

( Ts0)2Zn

275

DEAD 94%

Ph3P

'/,

/

OH Tetr Lett,

3,4461

(19C2)

S e c t i o n 139 Halides from Aldehydes No addi t i o n a l examples

.

S e c t i o n 140 Hal i d e s from A1 kyls

For t h e conversion RH

-+

RHal s e e S e c t i o n 146 ( H a l i d e s from

Hydri des )

JOC, 46, 2412 (19E1)

276

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 141

S e c t i o n 1 4 1 H a l i d e s a n d S u l f o n a t e s f r o m Amides No a d d i t i o n a l examples,

S e c t i o n 142 H a l i d e s f r o m Amines

6

4 4 N02

Ph

I

JCS P e r k i n

I 1890 and 2901 ( 1 9 8 0 )

t-BUS-N=O 9 84

CuC12, CH3CN N02 B u l l Chem SOC Japan,

1065 (1980)

B r (1) 1

1) NaN02, HC1

2 ) K2CO3’

53,

Et2NH

80%

3 ) Me3SiC1

1

L i B r o r NaI

C-CH3

C-CH3

11

0

I1

0

JOC,

46,

5239 (1981)

HALIDES FROM AMINES

SECTION 142

@

277

CH2NH2 ~50%

2) CH31 3)

c1

I

c1

Synthesis, 853 (1980)

UNP I2

90%

DMSO

Synth Comm, ll, 639 (1981)

GH,

1) HN02

2)

Ph-NH2

KOH

3) KI, H30CB

+

Ph-I

78%

Synthesis , 572 (1980)

ONH Ph

HF

Ph

-

H

93%

JOC, 45, 5328 and 5333 (1980)

4

278

COElPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 142

CuBr2, Me3CON0 99%

CH3CPI CH3

CH3

JOC,

5,2570

(1980)

S e c t i o n 143 H a l i d e s f r o m E s t e r s

AcovAc Me3SiBr

bAco@r ACO

CH2C1

AcO

100%

NHCOCH3

NHCOCH3

22, 513

Tetr Lett,

Me3Si I

:

( 1931)

u

I Y E t 0 4

Et O H

S y n t h Corn,

Jl,

763 ( 1 9 2 1 )

S e c t i o n 144 H a l i d e s f r o m E t h e r s and E p o x i d e s Me3SiBr

I CH20Ac

B r - ( CH2) 3-FH Br

S y n t h e s i s , 323 (1981)

37%

SECTION 145

HALIDES FROM HALIDES AND SULFONATES

279

1) Me3SiI 2) Cr03, H2S04 91%

Tetr Lett, 22, 1429 (1931) Section 145 Halides from Halides and Sulfonates

-

S03H

R- X r\ =

I2

Synthesis, 371 (1981)

1) LiCH2TePh 2) S02C12, Br2, or I2 3) looo, DMF

I

w

PPh3

-

f?-CH2X 59-95%

'1 alkyl Chem Lett, 1081 (1982)

G1%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

280

SECTION 146

S e c t i o n 146 Halides from Hydrides a-Halogenations of aldehydes, k e t o n e s , e s t e r s , and a c i d s a r e found i n S e c t i o n s 333 (Haloaldehydes) , 369(Haloketones) , 359(Haloe s t e r s ) , and 319 ( H a l o a c i d s ) .

OH

OH

I

CsS04F

70%

MeCN, B F 3 (ortho, para) JCS Chem Comm, 143 (1931)

cc1 I

99%

N02

JACS,

104,4680

(1982)

FH3

H OH !2 C$

CH 3 Tetr Lett,

21, 445

(1980)

SECTION 146

HALIDES FROM HYDRIDES

231

0 C-Ph

0 f-Ph

i1

I1

AS

N/

’$

0

COOMe

N

-e, C1CH2C1 ,/H20/H2SO4 CH3

COOMe Tetr Lett,

22, 3193 (19C1)

C12’ K2C03

CH2C1 80%

732

silica gel para:ortho

=

3.53

Chem Lett, 1423 (1900)

Me5Me Br2, HBr

60%

electrolysis

Sytith Comm,

Ph-CH2-CH3

Br2 La ( OAc)

w

Ph-CH-CH3 I Br

lo, 321

(1930) 90%

Bull Soc Chim France 11, 327 (1982)

282

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

FH3

SECTION 146

CH2Br CuBr2, t-BuOOH

I

9540

AcOH, Ac20

Br

Br

Synth Comm,

21,669

(1981)

NO,

88%

JOC, -46, 2169 (1981) HNSi Me

1) NBS/CC14

92%

2 ) MeOH

Q:. Br

2 moles

Br

Synthesis , 263 (1902)

93%

SECTION 146

HALIDES FROM H Y D R I D E S

233

Me0 9

r

B

-DMF Br2

J

-

H

H

Ph-H

m

S y n t h e s i s , 1096 ( 1 9 8 2 )

I2 A1C13, CuC12

*

Ph-I

79%

Chem L e t t , 1481 ( 1 9 8 2 )

CHO

CHO

e l e c t r o g e n e r a t e d I(33

74%

TFA

8 -8 A c t a Chem Scand

B y 34, 47 ( 1 9 8 0 ) c

1

PhI(OCOCF3)2

COOH

I2

COOH

JOC (USSR)

, 17,2320

(1982)

3 1%

284

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 146

I

Bull Chem SOC Japan, 54, 2847 (1981)

CF3COOI

77%

CH

I

CH3

Synthesis, 486 (1980)

Section 147 Halides f r o m Ketones

HF,

SF4 ~

OE t

OEt

85%

JCC (USSR), 17, 1260 (1981) PPh3, C12

Can J Chem,

91%

3,210

(1982)

SECTION 149

HALIDES FROM OLEFINS

235

S e c t i o n 148 H a l i d e s and S u l f o n a t e s from N i t r i l e s No examples.

S e c t i o n 149 H a l i d e s from O l e f i n s For h a l o c y c l o p r o p a n a t i o n s see S e c t i o n 74 ( A l k y l s from O l e f i n s ) .

w

HBr R4P@ BrO

88%

JOC, 45, 3527 ( 1 9 8 0 )

Ph 88% JOC, 45, 3573 (1980) I

C1 2NTs 73%

J Chem Res ( S ) , 376 (1981)

-

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

286

1) c-Hx~BH

0 II Ph-C-0

SECTION 149

+ 2 ) Chloramine-T ( X = C 1 )

o r Br2 (X=Br) o r IC1 ( X = I )

0

Ph-C-0 I'

X

X = C 1 , Br, I

nugo%

JOC, $6, 2582 and 3113 (1981) Synth Comm, 11,5 2 1 (1981)

Amberlyst A-26 (IC1:) 75% CH2C1

JCS Chem Conim, 1273 (1930)

MeOOC

MeOOC MeOOC

e l ec t r o l y s is NaBr, H2S04, H20/MeCN

-

MeOOC

x>'Br

92%

JOC, 46, 3312 (1931)

SECTION 149

HALIDES FROM OLEFINS

287

45% Tetr Lett,

Bu-CH=CH2

CH2C1 I

AIBN

2,4543

(1920)

31%

BU-CH-CH2-CH2 I I I c1

Bull Chem SOC Japan, -53, 770 (1980)

S e c t i o n 150 !la1 i d e s from Miscellaneous Compounds

&

c1 1 ) CH3MgX

2 ) - O H , NaOCl H 20/ E t O H S y n t h e s i s , 616 (1930)

Ph-B(OH)2

Na I ~

chlorami ne-T

-

, ,,

-

Org Prep Proc I n t ,

37%

14,359

(1982)

238

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

Review:

SECTION 150

"Methods o f F l u o r i n a t i o n i n O r g a n i c C h e m i s t r y "

Angew Chem I n t Ed, 20, 647 ( 1 9 8 1 ) Review:

" R a d i o i o d i n a t i o n Techniques f o r Small O r g a n i c M o l e c u l e s " Chem Rev, 82, 5 7 5 (1932)

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 11 PREPARATION OF HYDRIDES This chapter 1 i s t s hydrogenolysis and related reactions by which functional groups are replaced by hydrogen, e.g. RCH2X

-f

RCH2-H

or R-H Section 151 Hydrides from Acetylenes No examples of the reaction RCzCR

-f

RH occurs in the l i t e r a t u r e .

Section 152 Hydrides from Carboxyl i c Acids This section l i s t s examples of decarboxylation (R-COOH

-+

F-H) and

related reactions, 0 I1 Ph-C,

hv

N-H

acetone

0 I1

Ph-C,

N-H

+ C02

TCH’COOH

Synthesis, 141 (1932)

82%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

290

SECTION 153

Section 153 Hydrides from Alcohols and Phenols This section lists examples o f the hydrogenolysis o f alcohols and phenols, ROH

+

RH

1) Me3SiC1 , NaI 2) Zn, HOAc

-n-nonane 61%

Synthesis , 32 (1981) OH 91%

JCS Perkin I , 1207 (1980)

1) Bu3SnH, AIBN HO

2) Bu4NF 35%

JACS,

-lE932 , (1981)

SECTION 153

OH Ph-bH-Ph

29 1

H Y D R I D E S FROM ALCOHOLS AND PHENOLS

NaBH4-PdC1

* Ph-CH2-Ph

9 1%

Chem L e t t , 1029 ( 1 9 0 1 )

Ph3C-OH

Fe(W5

Ph3C-li

90%

t o 1 uene

Tetr Lett,

2,8 0 1

(1980)

1) N ,N ' - t h i o c a r b o n y l d i imidazole

~30-80%

2 ) Bu3SnH

(deoxy sugar)

R = p r o t e c t e d sugar

JOC,

26,

4843 ( 1 9 8 1 )

A l s o v i a H a l i d e s a n d S u l f o n a t e s , S e c t i o n 160

S e c t i o n 154 H y d r i des f r o m A1 dehydes No a d d i t i o n a l examples. F o r t h e c o n v e r s i o n RCHO A1 dehydes)

-+

RMe e t c . see S e c t i o n 64 ( A l k y l s f r o m

292

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 155

S e c t i o n 155 H y d r i d e s f r o m A1 k y l s T h i s s e c t i o n l i s t s examples o f t h e c o n v e r s i o n R - R ’

Ar-R

+

+

R-H or

Ar-H

“mNo2 Se02

dioxane

j.

0

*

70% N

Me

j.

H

T e t r L e t t , -21, 2433 (19GO) Zn/ZnCl

*

T e t r L e t t , -22, 695 ( 1 9 3 1 )

Section 156 H y d r i d e s f r o m Arnides

No a d d i t i o n a l examples.

SECTION 155

293

H Y D R I D E S FROM ESTERS

S e c t i o n 157 H y d r i d e s f r o m Amines T h i s s e c t i o n l i s t s examples o f t h e c o n v e r s i o n RNH2

-f

RH

0

0

II

I1

DMF 87% c1

c1

I n d i a n J Chem,

0 I1

CH2-CH-C-OMe

(1921)

0 I1

1) CH3C-OCHO

@if {jH2

m, 767

2 ) POCl,,

*

Et3N

3) Bu3SnH, AIBIJ

H

S y n t h e s i s , 68 (1980)

S e c t i o n 158 H y d r i d e s f r o m E s t e r s T h i s s e c t i o n l i s t s examples o f t h e r e a c t i o n s R C O O R ' RCOOR'

-f

R'H

-f

RH and

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS

294

VOL 5

0

SECTION 158

0

S y n t h e s i s , 119 ( 1 9 8 1 )

2.90%

JCS Chem Comrn, 732 ( 1 9 2 0 )

S e c t i o n 159 H y d r i d e s f r o m E t h e r s T h i s s e c t i o n l i s t s examples o f t h e r e a c t i o n R-0-R'

OM e

1) Me3SiC1, N a I 2 ) Zn, HOAc

+

+

R-H.

n-nonane

S y n t h e s i s , 32 (1981)

64%

-SECTION 160

295

HYDRIDES FROM HALIDES AND SULFONATES

CH20Me

LiBHEt3

rc

PdL4

CH3

JOC, 47, 4380 (1982)

S e c t i o n 160 Hydrides from Halides and S u l f o n a t e s

This s e c t i o n l i s t s t h e r e d u c t i o n s o f h a l i d e s and s u l f o n a t e s , RX

+

RH

PF

to1 uene, dicyclohexyl 18-crown-6

Tetr Lett,

2,2523

(2981)

WC’

NaBH4-PdC1 MeOH

Chem L e t t , 1029 (1931)

66%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

296

c1

SECTION 160

H

80%

S y n t h e s i s , 876 ( 1 9 3 2 )

LiBHEt3 b

PdL4

JOC,

Q

9, 4380

(1982)

OMe

OMe

Ni

N i C 1 2 , NaI

Ph3P 96%

DMF/H20

H

c1

JOC, 4 7 , 2622 ( 1 9 8 2 ) c

SECTION 160

Q

HYDRIDES FROM HALIDES AND SULFONATES

c1

297

c1 LiA1H4 9 2% ultrasound

H

Br

Tetr Lett, 23, 1643 (1932)

NaH, t-ArnONa 30%

Ni (OAc)2-WC16 JOC, 46, 1270 (19S1)

0

C1

1 ) Me3SiC1, NaI, CH3CN 2 ) aq. t h i o s u l f a t e

A

72%

JOC, 45, 3531 (1980)

aq. NaBH4 P.T.C.

-0 JOC, 46, 3909 ( 1 9 2 1 )

83%

298

COMPENDIUM OF ORGANIC SYNTtiETIC METHODS VOL 5

SECTION 160

Bu

31% Tetrahedron,

7, 2261

Angew Chem I n t Ed,

22,

(1931)

45 ( 1 9 3 0 )

NaH, i-AmONa

100%

ZnCl JOC,

46,

1270 ( 1 9 3 1 )

S y n t h Comrn,

12, 261

(1982)

SECTION 160

HYDRIDES

FROM

HALIDES AND SULFONATES

299

NaI, H2S04 9 5%

TH F/H20

Me0

Me 0

Tetr Lett, 21, 3195 ( 1 9 3 0 )

0

0 ISiMe3

89% CHCl Synth Cornrn, 11, 101 ( 1 9 8 1 )

0

0

Iron-graphi t e

94%

CH2Br

JOC,

0

47,

876 ( 1 9 8 2 )

0

n V

(Et0)2bJTeo Na'

56%

Et O H JOC,

47,1124

(1982)

300

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 160

p13

92%

o r P214 Tetr Lett,

(1981)

Pd(OAc)2

Br

P(g-Tol)3

OH

0

-cc13

K2C03

Tetr Lett,

Review:

2,1431

_23, 3085

87%

(1982)

"The H y d r o g e n o l y s i s o f O r g a n i c H a l i d e s " S y n t h e s i s , 425 ( 1 9 0 0 )

A s t u d y o f t h e r e d u c t i o n o f a l k y l h a l i d e s u s i n g LiAlH, JOC,

PhSO \2

/H

S?04

47,

-

i=c\

'gHll

CH3

P

'5"ll

i n THF.

276 (1982)

/7

Tetr Lett,

CH3

22,

3265 ( 1 9 8 2 )

28%

30 1

H Y D R I D E S FROM NITRILES

SECTION 163

Section 161 Hydrides from Hydrides

No a d d i t i o n a l examples,

S e c t i o n 162 H y d r i d e s f r o m Ketones No a d d i t i o n a l examples. F o r t h e c o n v e r s i o n R2C0

+

R2CH2 o r R2CHR' s e e S e c t i o n 72 ( A l k y l s

and M e t h y l e n e s f r o m K e t o n e s )

S e c t i o n 163 H y d r i d e s f r o m N i t r i l e s Bu,Sn ti s AIBN

:H3 CH3( CH2) 7-C-fIC CH7J

H: 3

91%

* CH3( CH2)7-CH I

CH J7 JCS P e r k i n I, 2657 ( 1980)

K/A1203

T

CN O

OE E t

t

88%

hexane

OE t JOC,

45,

3227 (1930)

COMPENDIUM O F ORGANIC SYNTHETIC METHODS VOL 5

302

GN

Ph

SECTION 163

KOH

92%

150'

H

H Synth Comm, -_ 10, 939 (1920)

S e c t i o n 164 Hydrides from O l e f i n s No a d d i t i o n a l examples

a

S e c t i o n 165 Hydrides from Miscellaneous CQmpOUndS

CH3( C H 2 ) 10-CH2SH

NaEt,BH 3

C H 3 ( C H 2 ) 10-CH3

7 3%

FeCl

Angew Chem I n t Ed,

jz,315 (1980)

2 2 , 1705 (1931) Tetr Lett, -

SECTION 165

HYDRIDES FROM MISCELLANEOUS COMPOUNDS

303

NH

/ 2 Me I Me-C-NO, I L Ph

N-CH2Ph

Me I Me-C-H

w

61%

I

Ph

JACS, 102, 2851 (1930)

w NO,

CN

92%

initiator

JACS,

103, 1557

(1981)

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 12 PREPARATION OF KETONES S e c t i o n 166 Ketones f r o m A c e t y l e n e s

cncl

r=rcl "-""

I

OH

1) PhHgOH, CHC13

-C-CH3 1\ 1l I

-

2) H20

- 0

l

JOC, 47, 3331 (1982)

OH

C=CH

Nafion-H H+

84% S y n t h e s i s , 473 (1981)

Ph-CrC-Ph

2 PhI(OCOCF3)2 C H C l 3/H20

+

00 I1

II

Ph-C-C-Ph

82%

D o k l a d y Chem, 245, 140 (1979)

KETONES

SECTION 166

FROM ACETYLENES

305

U

l i e l v Chim A c t a ,

t

L

"

co

H-CCC-Ph

'

54,2531

(1931)

Ph-C-CEC-Ph

t

-+ JCS Chem Comm, 333 ( 1 9 3 1 )

Bu33 t

C5H l - C ~ C H

2)

MVK, TiC14

3 ) $02

52%

Bu

'gHll

Chem L e t t , 2 2 1 ( 1 9 8 0 )

Ph2C0 t

BrCH2C-CH

0 1) Zn 2 ) HQ

73%

t

Ph S,ynth Comm,

lo, 637

(1920)

306

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 166

0 37%

2 ) NaOCH3

3 ) H202, NaOH S y n t h e s i s , 193 ( 1 9 8 2 )

S e c t i o n 167 Ketones f r o m C a r b o x y l i c A c i d s a n d A c i d H a l i d e s

6 OOLi

N

MgBr

+' Ph

rleo

C=NP1i2 c1 Tetr Lett,

0

86%

23, 5059

(1932)

Et3A1

Ph

Ph

J Gen Chem (USSR),

Hx3A1 t

0

A1C13 w

_51,1359

and 1434 ( 1 9 8 2 )

0 I1 Hx-C-Ph

66%

CH2C1

I!

Ph-C-C1

J Gen Chem (USSR) ,

20,2195

(1980)

S E C T I O N 167

KETONES FROM C A R B O X Y L I C A C I D S AND A C I D H A L I D E S

u-:' 0 I1

p

1) C 1 - A 1 - 0 I c1

307

0 i1 C-Et

*

87%

2 ) EtA1C12 J G e n C h e m (USSR) ,

BzBr

L2PdC1

t

0

Zn

,-

22,

1170 ( 1 9 8 2 )

0 I1

n-C8H17-C-Bz

78%

I,

n-C8H 7-C-C1 C h e m L e t t , 1135 ( 1 9 3 1 )

t

0 E t,C-COO'

3)

-co2

63%

J C h e m R e s e a r c h ( S ) , 44 ( 1 9 3 0 )

0 II

P h-C-TFIS

C H 3 1 , KF DMSO

0 I1

* Ph-C-Cti3 Tetr Lett,

55%

22,

1881 ( 1 9 8 1 )

308

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

gx

SECTION 167

0 0 Ch2=CH( CH2)*-C-C1

1) 0

I1

0 2 Ph-C-C1 I1

*

2 ) AcOH, H20

-

0

C H ~ = C H ( C H ~ ) ~ - C -3C H 35%

Indian J Chem, G , 504 (1981) Synth Comm, -10, 221 (1930)

00 Ph-C-C-Ph

Sm12

I1

II

78%

Tetr Lett, -22, 3959 (1981) r .

94-96%

JOC, 47, 300G (1982)

Angew Chem Int Ed,

19,822

(1980)

S E C T I O N 167

KETONES FROM C A R B O X Y L I C A C I D S AND A C I D H A L I D E S

309

CH3S03H

90% W

C

0

O

H JOC,

46,

2974 ( 1 9 G 1 )

1) P C 1 5 NHCOOR

2 ) A1C13

75% JOC,

46,

2431 (1981)

0

JOC,

45,

1046 (1930)

C h e m L e t t , 1501 (1980)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

310

SECTION 162

S e c t i o n 163 Ketones f r o m A l c o h o l s

Cr03 P.T.C. OH

OH

b

Tetr Lett,

G N.c rO

OH I

Ph-CH-CH3

(1980)

n

3. H c 1

83%

(on alumina) Synthesis

b

21, 4653

U

223 ( 1 9 8 0 )

po 1y ( v i ny 1 p y r id in iurn) d i chromate 69%

c y c l ohexane JOC,

K2Cr207

9, 1728

-

(1981)

0 ph-!-CH3

polyethylene glycol

S y n t h e s i s , 646 (1980)

22%

SECTION 168

KETONES FROM ALCOHOLS

POH OH I Ph-CH-CH,3

P;

CH2C1

(Bu4N)2Cr207 CH2C1

311

862

Synthesis , 691 (1930) 0 Ph-C-CH,3 It

w

30%

10, 75 (1930) Synth Comm, --

OH I Ph-CH-Ph

6

a

’-

[BzNEt3I2 Cr 0 HMPT

@

0 I1

PhHC\Ph

99%

Synthesis , 1091 (1982)

(Phen)CrOCl

94%

Tetr Lett, 21, 1583 (1920)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

312

0

OH

b

SECTION 168

95%

CH2C1

JOC, 47, 2790 (1982)

solid NaMn04 Tetr L e t t ,

2, 1655 (1921)

NaOCl , HOAc

4

JOC, 35, 2030 (1920) l e t r L e t t , 3 , 4647 (1922)

OH

85%

0

Ca (OC1) CH3CN

-6 Tetr L e t t ,

3, 35

93% (1982)

SECTION 168

KETONES FROM ALCOHOLS

3 13

82% Tetr L e t t ,

Q

CHOH I CH2Ph

23,

3135 (1982)

-Q OH

DDQ

di oxane

c=o I

CH2Ph

JOC,

45,

1596 (19GO)

Tetr L e t t ,

3,539

(1982)

electrolysis poly(4-vinylpyridine) CH3CN JOC,

45,

5269 (1980)

90%

314

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 163

electrochemical oxidation

T E A B , Me-S-Oct

0

35%

Tetr L e t t ,

1, 1867

(1980)

dPH dPH Ni(OH)2 e l e c t r o d e

+

HO

t-BuOH,

3

KOH

7 3%

0

Tetrahedron,

3, 3299 (1982)

Ni ( O B Z ) ~

86%

Br2

Synth Comm,

20,831

(1920)

SECTION 168

HO

&

3 15

KETONES FROF.1 ALCOHOLS

PhCH3, Raney NiA ,

Tetr Lett,

Ht , bentoni t e cl ay

& ?

21, 1071

(1980)

Y

I

65%

I

83%

S y n t h e s i s , 849 (1980)

100%

JOC, 47, 837 (1982)

C1S02NC0

85%

DMSO

S y n t h e s i s , 141 (1980)

316

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 168

(t-BuO)3Al 85%

t- BUOOH

OH

Tetr Lett, 21, 1657 (1980)

Bu N C1

4s0

Synthesis, 394 (1981)

2

0

JOC,

0 2 CH3CCH3 11

+

46,

1927 (1981)

93%

SECTION 162

KETONES FROM ALCOHOLS

3 17

RuCl 2L3

78%

PhIO or PhI(OAc)2

a\

Tetr Lett, 22, 2361 (1921)

(C1PPh2) 2Bi =O

*

85%

0

HO

Tetrahedron, 37, Suppl # l , 73 (1981)

Tetr Lett, -22, 2295 (1981)

. 7

t-BuOK

OH

-t-BUOH

t

Can J Chem,

J 58,

II 0 2730 (1980)

J3%

318

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

Tetr Lett, Related Methods:

23, 983

SECTION 168

(1982)

Aldehydes from Alcohols and Phenols ( S e c t i o n 48)

S e c t i o n 169 Ketones from Aldehydes

0 I1

RhCl L3

90%

JACS, 102, 190 (1980)

Pr-CHO Li

t

w

2 ) Rh(OAc)2 DME

I

+ 't

N2

0

Pr

JCS Perkin I , 2566 (1931)

"u

5 07;

SECTION 170

KETONES FROFI PIETHYLENES AND A R Y L S

319

1) Me3SiCN 2 ) LDA, BuBr

~ ~ 6 0overall %

Chem Ber,

113,3783

acHo

(1980)

n

CH2=CHCN

NaCN, DMF

Org Syn,

52,53

68%

(1930)

Section 170 Ketones from Methylenes and Aryls This section l i s t s examples o f the reaction R-CH2-R'

0 II

-+

R-C-R'

Q 0 'I

@

CH2CH3

'2'8-

-

C-CH3

cu

I1

(or CuS04 , peroxydi sul f a t e )

I

OMe

Indian J Chem, XlJ,

86%

OMe 153 (1921)

320

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

Tetr Lett,

m OMe

22,

SECTION 170

5127 ( 1 9 8 1 )

PdCl 2/CuC1 OMe

H20/DMF, O2

6 5%

Tetr Lett,

23, 2679

(1932)

1) B r 2 , E t 2 0 2 ) NaOH, THF/H20 65% Chem L e t t , 779 ( 1 9 8 0 )

,

@

FCr03 Q

H AcOH

0 S y n t h e s i s , 588 ( 1 9 8 2 )

98%

321

KETONES FROM AMINES

SECTION 172

Section 171 Ketones from Amides

No addi t i onal exampl e s . Section 172 Ketones from Amines

h

6

CHO !Q

CH3 DBU

-

JACS,

91%

104,4446

(1982)

100% Synthesis, 756 (1982)

H! 2

Ph-CH I

CH3

0

2 ) LDA 3)

II

(cooH)2

w

Ph-C-CH3

MeOH/THF/H20 JOC,

46,

1937 (1981)

58%

322

4

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 172

0 i1

Me4Sn, CO Pd(OAc)2

90%

c1

c1

Chem L e t t , 35 (1982)

S e c t i o n 173 Ketones from Esters

Ph

~~60%

Chem L e t t , 1483 (1979)

Bu-CC1 2 L i t

E t-COOMe

THF

Et20

0 I1 BuCCl 2 - C - E t

71%

Comptes Rendus ( C ) , 22, 105 (1980)

SECTION 173

323

KETONES FROM ESTERS

0

Bu2CuLi

I1

*

Ph-C-S

0I1 99%

Ph-C-Bu

JCS Chem Comm, 1231 (1981)

Me$ iOTf CH3CO0 96? Tetr Lett, 23, 2601 ( 1 9 8 2 )

Tetr Lett, 21, 3199 ( 1 9 8 0 )

0

c1

0

c1 Chem L e t t , 5 1 (1980)

c1 90%

324

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 174

S e c t i o n 174 Ketones f r o m E t h e r s a n d Epoxides

OBz JOC, 46, 1492 ( 1 9 8 1 )

6 &OoH

92%

S y n t h e s i s , 897 (1980)

0

1) Nay NH,

I .

3 ) H30f

Org Syn,

3,59

(1983)

PdL4

6 2%

Ph2PCH2CH2PPh2

JACS,

102, 2095

(1980)

SECTION 175

KETONES FROM HALIDES AND SULFONATES

325

9 7% PdCl 2-CuC1 6 0 T M S 21, 4283 ( 1 9 8 0 ) Tetr Lett, -

S e c t i o n 175 Ketones f r o m H a l i d e s and S u l f o n a t e s

Br I

Pr-CH-CH2

0

1) Me2N-@N-O_

II

2 ) DBU

B u l l Chem SOC Japan,

S02Ph

98%

Pr-C-CH3

54,

2221 ( 1 9 8 1 )

Mo05*py*HMPA 97%

TH F Tetr Lett,

1) B u L i PhCH2Ts

2) Pentyl B r 3) B u L i , CC14

w

Yenty1

Ph-C-TS I

c1

1, 3339

(1980)

TFA, AgC104

*

H2°

0 II

Ph-C- ( CH2)4CH3 B u l l Chem S O C Japan, 53, 3027 ( 1 9 8 0 ) I

326

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 175

0

[Bu3SnCH2COCH3] 9 1%

PdCl 2L2 OMe

OMe

Chem L e t t , 9 3 9 ( 1 9 8 2 )

'?"

1) C'H,

/SMe

S02Me

-270%

2 ) HC1, H20/MeOH Chem L e t t , 813 ( 1 9 8 2 )

PhS02-CLi 2-0 t

B r ( CH2)5Br

Ao70%

2 ) Ht 3 ) -OH

B u l l Chem S O C Japan,

23,

3619 ( 1 9 2 0 )

70%

T e t r L e t t , 21, 4687 (19GO) c

SECTION 176

KETONES FROM H Y D R I D E S

32 7

0

2k CH2Br

* 2 ) H30t 3 ) Pb(OAc)4

Chem Ber,

ro

PhCH=C, HNd Li

k

113,3706

CH2-C

.cH 65%

(1980)

2 ) NaI 3)

t

25%

Hp

B r ( CH2)4Br JCS Chem Comm, 1 1 2 1 (1931)

R e l a t e d methods:

Ketones f r o m Ketones ( S e c t i o n 1 7 7 ) , Aldehydes

from H a l i d e s ( S e c t i o n 55)

S e c t i o n 176 Ketones f r o m H y d r i d e s T h i s s e c t i o n l i s t s examples o f t h e r e p l a c e m e n t o f h y d r o g e n b y k e t o n i c g r o u p s , RH R2CH2

-f

-f

RCOR'.

F o r t h e o x i d a t i o n o f methylenes

R2C0 see S e c t i o n 170 ( K e t o n e s f r o m A l k y l s and M e t h y l e n e s )

328

COMPENDIUM

0

OF

ORGANIC SYNTHETIC METHODS VOL 5

0

SECTION 1 7 6

0

1)- O-E-O-O-t--Bu

II

CH2CCH3 55%

A

Synthesis, 761 (1982)

aoH aoH C1 CH2CN

BC13, A 1 C 1 3

*

85%

C - CH 2-C 1

C1 CH2CH2C1

II

0

JOC,

CH3COC1

6

EtA1C12

JOC,

0

1) CH3!-CN, 2 ) H20,

46,

139 ( 1 9 3 1 )

0 O=C-CH3

47,5 3 9 3

73%

(1982)

TiC14

2.90%

-OH T e t r L e t t , 22,

c

1171 (1981)

329

KETONES FROM KETONES

SECTION 177

0

0

1) F ' d - C l , A 1 C 1 3 2 ) NaOH, H20/dioxane

I

S02Ph

96%

H

T e t r 1. e t t ,

22, 4901

(1981)

S e c t i o n 177 Ketones from Ketones This s e c t i o n c o n t a i n s a1 k y l a t i o n s of ketones and p r o t e c t e d k e t o n e s , ketcne t r a n s p o s i t i o n s and a n n e l a t i o n s , ring expansions and r i n g openings , and d i m e r i z a t i o n s .

Conjugate r e d u c t i o n s and Michael

a l k y l a t i o n s o f enones a r e l i s t e d i n S e c t i o n 74 ( A l k y l s from Olefins). For t h e p r e p a r a t i o n of enamines from ketones s e e S e c t i o n 356 ( Ami ne-01 e f i n )

Q

. 72%

OTMS

Chem Ber,

113,3734

and 3741 (1980)

330

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 177

JACS, 104, 6031 ( 1 9 3 2 )

PhCH2Br t -

BzMe3N

F

JACS,

Review:

py

104,1025

CH2Ph

(1982)

" L e w i s A c i d I n d u c e d a-A1 k y l a t i o n of Carbonyl Compounds" Angew Chem I n t Ed,

N

73%

,"\

1, 96

(1982)

1) LDA, THF I

OMe

82%

~~~

2) E t I

94% ee

JACS,

103,3031

and 3088 ( 1 9 3 1 )

SECTION 1 7 7

OBBu2 I BuCH=C-CH3

331

KETONES FROM KETONES

Me2NCH2CH20Li BzBr

*

0I1 Bu-CH-C-CH I

Bz S y n t h Cornm,

70%

3

lo, 139

(1980)

JOC,

46,

JOC,

47, 5 0 9 9 ( 1 9 8 2 )

i'etr

Lett, 23, 3 0 7 3 ( 1 9 8 2 )

3771 (1981)

CH2C1

332

COMPENDIUM O F ORGANIC SYNTHETIC METHODS VOL 5

0

SECTION 177

00Li'

t

H2C=C,

,NMePh

2 ) Me1 79%

3) H30f

CN

Synthesis , 413 (1980) OTMS

1) H ~ C = ~ - C H ~ C I 2 ) (COOH)2,

H20

+@

82%

JOC, 46, 4631 (1931) c

Org Syn,

60,

117 (1921)

SECTION 177

KETONES FROM KETONES

1) LDA

333

2 ) Cu(OTf)2 45-73%

o r FeC13, DMF/THF

c

Chem Pharm B u l l JOC,

$5, 5408

,8,262

(1980)

(1980)

Tetr Lett,

3, 3595

(1982)

1) CH3Li, ZnC12

0

H-?-CH2SePh

2 ) E t 3 N , MeS02C1 H

B

JOC,

47, 1632

(1982)

1) LDA w

2)

*OEt QFP

JOC,

46,

4103 (1981)

93%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

334

SECTION 177

n

Synth Comm, lJ, 217 (1981)

OLi

t

/o

Ac 0

3CS Chem Cornm, 1159 (1981)

2) B E t 3

1

Ac 0

81%

JOC,

47,3133 (1932)

SECTION 177

335

KETONES FROM KETONES

78%

943

21, 1205 (1980) Tetr Lett, /

TMS

1) Me2C=C H' 2) SnC14 3) RhC13

3

COC 1

-

dj, 70%

JOC, 45, 3017 (1980) Me3Si CHN2

BF3 * Et20

-b

70%

Chem Pharm Bull, 20, 119 (1982) Tetr Lett, 21, 4619 (1930) c

336

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

Q

SECTION 177

0

SnC14

80%

h

benzene

OMe

OMe Tetr Lett, 1_1, 1887 (1930)

t

Ph

N02

N02 Synthesis, 467 (1982)

JOC,

45,

2919 (1920)

SECTION 178

337

KETONES FROM NITRILES

OLi

Ph

A

Ph I

o=c

I

t

9 1%

0 3ePh

w

JOC, 45, 2921 ( 1 9 2 0 )

50H21

( PhSeO) 2O 89%

JCS P e r k i n I, 1650 ( 1 9 8 0 ) Ketones may a l s o b e a l k y l a t e d and homologated v i a o l e f i n i c k e t o n e s ( S e c t i o n 374) R e l a t e d Methods:

Aldehydes f r o m Aldehydes ( S e c t i o n 4 9 )

S e c t i o n 178 Ketones f r o m N i t r i l e s 'OH,

O2

0 0 Et3NBz C1

w

KO

Ph

S y n t h e s i s , 1009 ( 1 9 2 0 )

84%

338

COMPENDIUM

OF

ORGANIC SYNTHETIC METHODS VOL 5

SECTION 1 7 8

CH3CH2CH2CN

+

1) Z n ( A g )

80%

2 ) NH4C1 , H20

wBr

Tetr Lett,

2, 6 4 9

(1931)

1) LDA

2) E t B r

0

*

3 ) H20 Ph-CHZCH-CHCN

73%

4 ) C U ( O A C ) ~ ,i t O H 1 ) H C 1 , CH30H

Bz-CN

11

Ph-CH=CH-C-Et

2)

f-$

0

3 ) HC1

Chem L e t t , 1263 ( 1 9 8 2 )

011

Et3N

Bz-C-CH~

+

53%

S y n t h e s i s , 130 (1981)

1) NaHMDS 2 ) H30t 3 ) NaOH

Tetr Lett,

-3 c

22,

1359 ( 1 9 E l )

855

SECTION 179

339

KETONES FROM OLEFINS

S e c t i o n 179 Ketones from O l e f i n s

L

JCS Chem Comm, 1274 (1981)

0 Hx

0

Na2PdC1 Hx

t-BUOOH

0

A A

59%

Chem L e t t , 257 ( 1 9 3 0 )

-A

‘gH 13 X

=

-

PdC12, C u C l

H20/di o x a n e

, O2

1

0

Me, OMe

Chem L e t t , 859 ( 1 9 3 2 )

4 X 61%

340

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 179

(aB

1) ( PhS)3C-Li 80%

2 ) NaOH, H202 JCS Chem Comm, 1149 ( 1 9 8 1 )

1) Bu-CzCBr BBr

2 ) NaOMe C-CH2Bu

81%

JOC, -47, 754 ( 1 9 8 2 )

0

‘d- ( c H ~ )1

~ ~ 3

2 ) CH3(CH2)9CH=CH2 67%

3) c a r b o n y l a t i o n JOC, 45, 4540 and 4542 (1980)

1) 03, MeOH

77%

2 ) (NH2)2C=S

CH ( OMe)

MeOH Tetrahedron,

3,3013

(1982)

SECTION 180

34 1

KETONES FROM MISCELLANEOUS COMPOUNDS

h v , 02 54%

FeCl 3, p y r i d i ne JOC, 46, 509 (1981) c

R e v i ew :

"Ozonol y s i s

--

Modern Method i n t h e C h e m i s t r y o f

01 e f ins 'I Russ Chem Rev,

50,

636 ( 1 9 8 1 )

See a l s o S e c t i o n 134 ( E t h e r s a n d E p o x i d e s f r o m O l e f i n s ) and S e c t i o n 174 ( K e t o n e s f r o m E t h e r s and E p o x i d e s ) .

S e c t i o n 180 Ketones f r o m M i s c e l l aneous Compounds C o n j u g a t e r e d u c t i o n s and r e d u c t i v e a1 k y l a t i o n s o f enones a r e l i s t e d i n S e c t i o n 74 ( A l k y l s f r o m O l e f i n s ) .

1) NaH

91%

2) KMn04

JOC, 47, 4534 ( 1 9 8 2 )

342

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 180

S y n t h e s i s , 44 and 6 6 2 ( 1 9 3 0 )

I ) LDA

* 2 ) Mo05.pyr*HMPA Tetr Lett,

a:H3 85%

22,

5235 ( 1 9 8 1 )

99%

B u l l Acad USSR Chem,

31, 211

(1922)

%BU3

Me0C = C H OMe

*

t

EtOS02F

0

Bu-C-CH2Et

2 ) H30t Chem L e t t , 1059 (1981)

89 ?;

SECTION l8OA

343

PROTECTION OF KETONES

Angew Chem I n t Ed, 20, 395 (1981)

Bz

CH3MgI

~~t~cH2)7cH3 I@

Me

+

0 CH3 I1 I C H ~ - C - C H ( C H ~7) ~

~

3

83%

10 JCS Chem Comm, 282 (1982)

S e c t i o n 180A P r o t e c t i o n of Ketones See S e c t i o n 362 f o r t h e formation of enol e s t e r s and S e c t i o n 367 ( E t h e r - O l e f i n ) f o r t h e formation o f enol e t h e r s .

Many o f t h e

methods i n S e c t i o n 60A ( P r o t e c t i o n of Aldehydes) a r e a l s o a p p l i cab1 e t o k e t o n e s .

344

COMPENDIUM

OF O R G A N I C

SYNTHETIC METHODS VOL 5

SECTION 130A

n

OTMS

0 0 \ /

AR '

R

0 I1

R-C-R'

>90% y i e l d

R

Tetr Lett,

1, 1357

R'

(1930)

n

HOCH2CH20H

98%

p o l y v i n y l p y r i d i n e HC1 resin B u l l Chem SOC Japan,

n

0 R

\

/

C / \

0

L i B F 4 , w e t CH3CN

54,

309 (1981)

0 P

I1

.ago%

R/'\RI

R'

A l s o removes d i m e t h y l and d i e t h y l k e t a l s . S y n t h Cornrn,

12,267

(1982)

SECTION 180A

Me0

R

R'

PROTECTION OF KETONES

'2'4 or PI3

345

0

70- 90%

I1

R

Angew Chem Int Ed, 2,1006 (1930)

R

=

Me, Et, -(CH2)2

J Chem Res (S), 243 (1982)

OMe

Me0

90%

Me OMe

Me Me0

0

JOC,

,OTMS

1) Me-CH=C,

Bu4NF

0

II

R-C-CH2R'

2 ) ,'H

$5, 3422

0Ele

HYCH2CH2YH (Y = 0, S )

*

(1980)

nY

Y

R

\

I

C

/ \

CH2R'

Synthesis, 1089 (19212)

43-66%

346

COMPENDIUM

0

OF

O R G A N I C SYNTtiETIC METHODS VOL 5

HC( OMe)

II

R-C-R'

*

Me0

\ /

C

/ \

SECTION 130A

OMe "u

90- 100%

I Nafion-H,

CC14

R

R'

I

s

HSCH2CH2SH

N a f i o n - H , benzene

7

~80-100%

/L\

R

R'

S y n t h e s i s , 232 ( 1 9 8 1 ) Review:

"Methods f o r t h e P r e p a r a t i o n o f A c e t a l s f r o m A l c o h o l s o r O x i r a n e s and Carbonyl Compounds" Synthesis, 501 (1981)

SO2, benzene HSCH2CH2SH

P

S

R

R'

0 II

50-80%

R-C-R' I

HSCH2CH20H

\ /

/c

R

\

R'

Synthesis, 831 (1982)

SECTION 180A

PROTECTION

0

OF KETONES R" S

2R"SH

II

+

R-C-R'

A1 C1 R"

a1 k y l

,

347

R

dithiol

\

0

SR"

C

0 \

100%

"u

R'

Tetr Lett, 21, 4225 ( 1 9 8 0 )

HI04 steroid

I

CH?C1 ?/MeOH -

-

,93%

2

JCS Chem Cornm, 286 ( 1 9 3 0 )

sn s

+

\J

,

aryl

f\

s

cyclic

S y n t h e s i s , 965 ( 1 9 8 2 )

o r MeS(SMe):SbCl6 -

0 >

/I

R-C-R'

69

'R'

R, R ' = a l k y l

,

HC1 , H20/DMSO/di SO/di oxane

\C'

R'

6 5- 9 9 Z

DMSO

R, R ' = a1 k y l

s

0 I' R-C-R'

Me3SiI ( o r B r )

,

aryl

S y n t h e s i s , 679 (1982)

>95%

COMPENDIUM

348

n

S

\ C2

OF

O R G A N I C SYNTHETIC METHODS VOL 5

/ \ R R'

0I '

1) Me30BaBF4

2)

SECTION 18OA

*

Hp

R-C-R'

..go%

S y n t h e s i s , 135 ( 1 9 8 1 )

n

s

' 'R

C'

s

'R'

-

Pb02, H20 BF3.THF

0 II R-C-R'

80-96%

S y n t h e s i s , 580 ( 1 9 8 2 )

m s s ' r / / L \

R

R'

HgO 35% aq. HBF4

0 'I

R-C-R'

~ 8 0 100% -

Synthesis, 5 1 (1981)

65-92% IL\

R

R'

JOC, 47, 2212 ( 1 9 8 2 )

SECTION 180A

ns s

PROTECTIOK

OF KETONES

( PhSe0)20

*

349

0 I' R-C-R'

\ I

R

C 0 \

JCS P e r k i n I, 1654 ( 1 9 8 0 )

R'

n

S

electrochemical oxidation

Tetr Lett,

n \c

*

R-C-R'

85-97%

(F-TOl ) 3 N

R

S

0II

3,5 1 1

(1980)

0

C 1 S02F

'I

R-C-R'

ether/H20

56-36%

I \ R R' S y n t h e s i s , 146 ( 1 9 6 1 )

n S\ c / s R0 \ R '

1) HC1 , 2) H202

*

o r t r i c h 1o r o i socyan u r i c ac id , AgN03, MeCN/H20

0 I'

R-C-R' 65-98%

S y n t h e s i s , 657 and 659 (1980)

350

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

0

R", N

R"NH2

I1

-

*

R-C-R'

Bu2SnC1

SECTION 180A

A

>80%

i1

R

R'

S y n t h Cornm, -12, 495 ( 1 9 8 2 )

0 NH20H

1, 1425

Tetr Lett,

6

OH, N

0

N

P o r a s i l , 194'

0\

R'

LJ

JACS, 102, 1453 ( 1 9 8 0 )

Na2S204

C

R

A

/OH

I1

(1980)

0 11

R-C-R'

H2° A u s t J Chern,

32,

201 (1979)

2 C%

SECTION 180A

6

PROTECTION

O,H

N

/OH

I1

C

0\

R

R'

NaOH, H202

MeOH/H20

OF

KETONES

351

-6 S y n t h Comm,

20,465

89%

(1980)

0I1

P.C.C.

*

55-85%

R-C-R'

H202, a c e t o n e S y n t h e s i s , 125 (1980)

b /OH

N

0 x

I1

1) VC12 4

2 ) H30t

b

87%

S y n t h e s i s , 220 (1980)

( PhSeO) 2O

0

*

I1

R-C-R'

pa

ROc\R '

X = OH, NHPh

JCS P e r k i n

I , 1212 ( 1 9 8 0 )

7 0- 9 0%

352

COMPENDIUM

OF ORGANIC SYNTKETIC METHODS VOL 5

OAc

SECTION 1 8 0 ~

OAc

S y n t h Comrn, -1 2 , 15 ( 1 9 8 2 )

HOAc

0 H2N-C-NHN

2 ) O' H

Tetr L e t t ,

21, 6 5 1

(1980)

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 13 PREPARATION OF NITRILES S e c t i o n 181 N i t r i l e s f r o m A c e t y l e n e s No a d d i t i o n a l examples.

S e c t i o n 182 N i t r i l e s f r o m C a r b o x y l i c A c i d s and A c i d H a l i d e s

COOH

1) C1S02NC0 2)

CH 3

2.60%

DMF, 20'

100% ee

CH3 S y n t h Comm,

0 It

H2N-S02-NH 120°

2

12, 2 5

(1922)

-6

( S l i g h t l y lower y i e l d s s t a r t i n g from the acid) Tetr Lett,

2,1505

(1982)

9 5%

354

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 133

Section 183 m i l e s from Alcohols Bu3P, KCN

n-C8H, 7-OH

*

CCI4, MeCN

76%

n-C8H17-CN Synthesis , 1007 (1 980)

NH,3

n-C7Hl 5-CH20H

Cu, 300'

n-C7H1 5 - C ~ N -

JOC,

(y OH

9, 754

(1981)

NaCN , Me3SiC1

30%

NaI, DMF/MeCN

JOC,

87%

46,

29G5 (1981)

Section 184 Nitriles from Aldehydes C7H, 5CH0

-

NH20H HC1 pyridi ne/tol uene

*

C 7H 15-C=N Synthesis, 190 (1982)

82%

NITRILES FROM ALDEHYDES

SECTION 184

Ph-CHO

EtN02

+

pyridine/HCl

355

Ph-CrN

80%

Synthesis, 739 (1981)

C H (CH& ~ 7~~~

diphenyl free sulfimide

Tetr Lett,

Ph-CHO

Ts-CH2-NC

t-BuOK, DME

CH3(CH2)7-CgN

21, 761

(1980)

Ph-CH2CN

+

78%

67%

Synth Comm, lo, 399 (1980)

C5H1 -CH=NOH

C1 S02F

Et3N

+

C5H11-C-P.I

92%

Synthesis, 659 (1980) 0

Ph-CHO

98%

A

Synthesis, 702 (1980)

356

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

NOH

m

SECTION 1 8 4

0

C-N

"

kN-C-CF3

9 5%

B u l l Chem SOC J a p a n , 54, 1579 (1981)

Ph

1

Ph C7H 15-CH=NOH

SMe

B ~~0

*

C7HI5-CrN

S y n t h e s i s , 1016 ( 1 9 8 2 )

H I

C=NOH

T e t r L e t t , 22, 1 5 9 9 ( 1 9 8 1 ) c

86%

SECTION 185

NITRILES FROM ALKYLS, METHYLENES, AND ARYLS

357

Ph2S=NH

252

ciio S y n t h e s i s , 1005 ( 1980)

-

1) (TMS) 2C=C=N-TMS

CHO

BF 3* E t 2 0 2 ) NaOH, MeOH

JCS Chem Comm, 56 ( 1 9 8 2 )

0 11

Ph-C-CHO or

Ph

0 11

* Ph-C-CN

0 11

Ph-C-CH2Br

S y n t h e s i s , 844 (1980)

S e c t i o n 185 N i t r i l e s from A l k y l s , M e t h y l e n e s , and A r y l s No a d d i t i o n a l examples.

9 7%

358

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 186

Section 186 Nitriles from Amides

0

Synthesis, 591 (1982)

1) Me2N=CC12

Me02C ‘ONH2

+

2) pyridine

CN

Synth Cotnm,

s

I1

C1 1H23-C-NH2

Me02C

LO, 479

90%

(1980)

(Bu3Sn)20 or Bu2Sn0 * C 1 1 H 23-CEN . JOC,

47,4594

77%

(1982)

Section 187 Nitriles from Amines C9H1 9-CH2-NH2

N i (OH)*-anode H20, KOH

+

CgHl9-C5N

Synthesis, 145 (1982)

91 %

SECTION 190

Ph-CH2NH2

NITRILES FROM HALIDES

-

Ph

Ph

2) Me1 3) NaCN, DME

PhCH2CN

3 59

80%

Synthesis, 711 (1981) Section 188 Nitriles from Esters

No additional examples. Section 189 Nitriles from Ethers and Epoxides No additional examples. Section 190 Nitriles from Halides

n-C8H 17Br

benzene

t

-. n-C8HI7-CN

Uses a cationic resin loaded with cyanide. Synthesis , 299 (1980)

90%

360

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 190

20, 1017 ( 1 9 8 1 ) Angew Chem I n t Ed, -

Br

CN

KCN

*

NiBr2L2-Zn-PPh3

85%

Chem L e t t , 1565 (1982)

7 9%

JACS,

Bu3SnCN

*

104,1560

(1982)

92%

LCN

Tetr Lett,

1, 2959

(1980)

SECTION 191

NITRILES FROM H Y D R I D E S

36 1

S e c t i o n 191 N i t r i l e s f r o m H y d r i d e s

(CN12

-50%

RF plasma CH3

CH3 JACS,

Ph

COOEt

102, 7119 Ph

1 ) 30% H202,MeOH

2 ) TFAA, CH2C12

*

3 ) KCN, H20

(1980)

COOEt 73%

QClj

Me

Me S y n t h Comm,

lo, 495

(1980)

Ph3P (SCN)2

JCS P e r k i n

I,

1132 ( 1 9 8 0 )

362

COMPENDIUM

OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 191

1 ) LDA 2 ) PhCH2SCN

*

&CN

70

0 Comptes Rendus,

291, 179

(1980

CN

Li

I

I

C

C Ill C

111

C

92%

S y n t h e s i s , 150 (1980)

S e c t i o n 192 N i t r i l e s f r o m Ketones

2 ) KCN, MeOH 72%

JCS P e r k i n I , 1487 (1980)

S E C T I O N 193

NITRILES FROM NITRILES

363 CN

1 ) TMSCN, Zn12

82%

2 ) P0Cl3, p y r i d i n e

Chem L e t t , 1427 (1979)

1 ) Me3SiCN,

Ph2C=0

Zn12

Ph C

2 ) H30+, THF

O,H 'CN

60,

Org Syn,

1 4 (1981)

S e c t i o n 193 N i t r i l e s f r o m N i t r i l e s C o n j u g a t e r e d u c t i o n s and M i c h a e l a l k y l a t i o n s o f o l e f i n i c n i t r i l e s a r e f o u n d i n S e c t i o n 74 ( A l k y l s f r o m O l e f i n s ) .

Ph-CH2CN

Et O H

RuH2L4

Et I

Ph-CHCN

92%

Tetr Lett,

ArCHO t

A r I CH2CN

1)

-OH

2 ) NaBH4,

DMF

-

2, 4107

ArCH2CH-CN I

Ar'

JOC, 45, 171 (1980)

(1981)

80-90%

364

COMPENDIUM

OF O R G A N I C S Y N T H E T I C METHODS VOL

CN

Me0 1)

5

SECTION 193

CN

C0,Et

LDA 76%

JOC,

PhCH2CN t

Ph-CHO

45,

2614 (1980)

Ph

52% NaOH/H20

*

t o 1 uene/PEG

\

71 %

NC

S y n t h e s i s , 913 (1981)

S e c t i o n 194 N i t r i l e s f r o m O l e f i n s

84%

CN JACS,

104,6449

(1982)

S E C T I O N 195

N I T R I L E S FRON MISCELLANEOUS COMPOUNDS

Section 195 N i triles from Miscellaneous Compounds No additional examples.

365

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 14 PREPARATION OF OLEFINS

S e c t i o n 196 O l e f i n s f r o m A c e t y l e n e s

Bu

HZ

BU-C %-BU

98%

N i on K / g r a p h i t e JCS Chem Comm, 540 (1981)

JOC,

46,

5340 and 5344 (1981)

w

Zn (Cu)

Ph m

Ph-C:C-Ph

MeOH, A Tetr Lett,

C5H11-C:C-C

H

NaAl H4 NbC15

H ‘gHll

‘cq‘

Ph

21,

’

’95%

1069 (1980)

H “gHl1

Chem L e t t , 157 (1982)

62%

OLEFINS FROM ACETYLENES

SECTION 196

367

76%

2) NaOMe 3) CH3COOH

JOC, 47, 754 ( 982) JOC, 47, 3808 1982)

Synthesis, 195 1982)

Bu

m ( s i a ) 2 t

PhCH2Br

NaOH

*

PdL4

w

Bu

CH2Ph

99%

Tetr Lett, 21, 2865 (1980) Bull Chem SOC Japan, 53, 1670 (1980) BBr2*SMe2

1 ) H-C-C-Pr

2) NaOMe

3 ) 12

0

w

H\

c=c,H,

74%

Ph

JOC, 47, pages 171 , 3806, and 5407 (1982) 61%

Tetr Lett,

1, 5019

(1980)

368

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5 CH20SOMe C C I

XI:

[BuCuBrIMgCl .LiBr THF

111

I

CH20SOMe

I

I

Br

Ph-ZnC1 PdL4

Me.

Me

80-95%

* /

Rec Trav Chim Pays-Bas, Me Me-C-CzC-H

SECTION 196

99,340

,C=C=CHPh

Tetr Lett,

(1980)

80-95%

22, 1451

(1981)

Review: "Carbometal lation (C-metallation) o f A1 kynes: Stereospecific Synthesis o f A1 kenyl Derivatives"

Synthesis, 841 (1981) Section 197 Olefins from Carboxylic Acids

+ 'CHCOP t

+CHO

~60%

2 ) PhS02C1 , pyridine 3) a

JOC,

9, 3359

(1981)

OLEFINS FROM ALCOHOLS

SECTION 198

369

Section 198 O l e f i n s from Alcohols

OH

DCC

94%

CuC1, e t h e r

S y n t h e s i s , 1017 (1982)

5

COOMe

Ph3P

OH

{YOH OH

S

___)

O

o

M

cc1

Z Chem,

3, 372

(1980)

C 1 SiMe3 ~

Na I

ao-ga%

L

Tetr Lett,

e 7 5%

3 , 1365

(1982)

370

SECTION 198

CONPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

1 ) C12C=S DMAP 2)

*

n

Me-N,p.il-Me I

Ph

M . )

Tetr L e t t ,

23,

0

81 %

1979 (1982)

TiCl 3/LiA1 H4

7 5%

THF

JACS,

0 11

Ph2P

HO

xy#Cl H

-

3 C H3

104,5807

(1982)

NaH

DMF

Ple

CH2CH2CH3

Me

63%

Tetr Lett,

3,4505

(1982)

SECTION 199

OLEFINS FROM ALDEHYDES

371

S e c t i o n 199 O l e f i n s f r o m A l d e h y d e s Ph

2 ) H',

-h

BF3*Et20

TMS

W

78% COOMe

0 f

Ph-CHO

similar

Ph

260%

HMPT JCS Chem Comm, 877 ( 1 9 8 1 )

Ph-CHO

S y n t h Comm,

11,125

(1981)

1 ) B u L i , R2CH0

1 ) B u L i , R2C02Et I

JCS Chem Comm, 100 (1981)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

372

Ph

SECTION 199

4 nCH0 t

cH c H = c H

i i C =C1-1 - C H = C i i

50% NaOH

2 78%

c1

c1

Tetr Lett, 21, 1 3 7 5 ( 1 9 8 0 )

Tetr Lett, 21, 4021 ( 1 9 8 0 )

0

bl (OEt) 2

Z-NH-CH-COOEt

)- CKO -

B0

Angew

I,

Z-NH-C-COOEt

80%

Chem Int Ed, 21, 776 ( 1 9 8 2 )

SECTION 199

OLEFINS

FROM ALDEHYDES

373

A -

!!.-c7H1 5

.60%

t

n-C7H,5-CH0 "c7H1 5 Tetr Lett, 22, 2751 ( 1 9 8 1 )

OMe

4

Ar

AsPh3 I1

c1

-+

JOC, 46, 4292 ( 1 3 8 1 )

ArCHO

40-80%

c1

I n d i a n J Chem, 18B, 359 ( 1 9 7 9 )

374

Me0

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

DCH0

SECTION 199

K2C03

t

n

Me0 0

Me

62% J Chem Research

( S ) , 106 ( 1 9 8 1 )

NaOH -I

EtOH

Ph-CHO

Me

Synthesis, 647 ( 1 9 8 0 )

Ph

OLEFINS FROM ALKYLS, METHYLENES, AND ARYLS

SECTION 200

PhCH2CH2CH0

LiI

+

*

ether

0

375

2hCH2Ci12

CH3

I,

CH3CCH3

75% JCS Chem Comn, 486 ( 1 9 8 0 )

t

GCHCN

@-@

CH$Me3 JCS P e r k i n I , 2516 (1'380)

R e l a t e d Methods:

" O l e f i n s f r o m Ketones ( S e c t i o n 207)

S e c t i o n 200 O l e f i n s f r o m A l k y l s , M e t y y l e n e s , and A r y l s T h i s s e c t i o n c o n t a i n s d e h y d r o g e n a t i o n s t o f o r m o l e f i n s and u n s a t u r a t e d k e t o n e s , e s t e r s , and amides. s i o n of aromatic r i n g s t o o l e f i n s .

It a l s o includes t h e conver-

Hydrogenation o f a r y l s t o

a l k a n e s and d e h y d r o g e n a t i o n s t o f o r m a r y l s a r e i n c l u d e d i n S e c t i o n

7 4 ( A l k y l s , M e t h y l e n e s , and A r y l s f r o m O l e f i n s ) .

376

COMPENDIUM

OF

ORGANIC SYNTHETIC METHODS VOL 5

SECTION 200

(ase); Br2 *

l) 2 ) RaIo4

-CHO

9C%

Also works w i t h k e t o n e s . Tetr Lett, 23, 2105 ( 1 9 8 2 )

1 ) NaH 2 ) Se 3 ) Me1

-

83%

4) H202 Tetr Lett, 22, 3043 (1981 )

85%

JGC, 4 6 , 2920 (1981 )

100%

Aus'c J CIiem, 3 3 , 1537 ( 1 9 8 0 )

OLEFINS FROM ALKYLS, METHYLENES, AND ARYLS

SECTION 200

377

Co'salicylidene 02, MeOH

H

H

Chem L e t t , 1287 ( 1 9 8 0 )

1 ) H-C-C-TS 2 ) NaH2P04 Fle 0 H / T H F

35%

JCS Chem Conm, 633 ( 1 9 8 0 )

A ' 2'3

2

6

63% S y n t h e s i s , 60 ( 1 9 8 2 )

(HCHO) CF3COOo MefHpPh .80-90%

Ora Svn. 60. 8 8 ( 1 9 8 1 )

378

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

P 0

SECTION 200

1 ) 2 LDA 2) (MeOCSS)2

55%

3) ZnC12 4) BuCHO

0

d?

(E isomer is formed in 58% yield if ZnC12 is omitted.)

B

0

Chem Lett, 595 (1980)

H2C ( OMe ) POC13/NaOAc

0

CH2

70%

Synthesi s, 34 ( 1982)

Related methods: Alkyls and Aryls from Alkyls and Aryls (Section 65) Alkyls and Aryls from Olefins (Section 74)

Section 201 Olefins from Amides

90%

Tetr Lett, 22, 199 (1981)

SECTION 203

OLEFINS FROM ESTERS

379

S e c t i o n 202 O l e f i n s f r o m Amines

An a l t e r n a t i v e t o t h e Hofmann e l i m i n a t i o n .

-0

90%

JCS Perlcin I , 2347 ( 1 9 8 2 ) JCS Chem Comm, 95 (1981

S e c t i o n 203 O l e f i n s f r o m E s t e r s Cp2TiCH2A1C1Me2

85% CH2

JACS, 102, 3270 ( 1 9 8 0 )

eo 3

1 ) DIBAL-H

2 ) Ph3P=CH2

55%

3 ) H+ S y n t h e s i s , 1015 ( 1 9 8 0 )

380

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 203

I-II

CH3CN V

JACS, 104, 5844 ( 1 3 8 2 )

S e c t i o n 204 O l e f i n s f r o m E t h e r s and E p o x i d e s

O-OMe

w

Silule3

95%

TiC14, C H 2 C 1 2

JOC, 47, 2436 ( 1 9 8 2 )

Ph3P* HI

+

Ph3P12

S y n t h e s i s , 828 ( 1 9 8 0 )

>95%

SECTION 204

OLEFINS FROM ETHERS

AND

EPOXIDES

381

96%

Tetr Lett, 21, 1173 ( 1 9 8 0 )

Me3Si I NaI

-n

92%

Tetr Lett, 22, 3551 (1981 )

wc 1 THF

3rg Syn, 60, 29 ( 1 9 8 1 )

NbCl 5/NaA1 Hq

53%

Chen L e t t , 157 ( 1 9 8 2 )

382

COMPENDIUM

OF

ORGANIC SYNTHETIC METHODS V O L 5

-0

0

I1

(Et0)2P-TeLi

JOC,

SECTION 204

25,

88%

2347 (1980)

-

S e c t i o n 205 O l e f i n s f r o m H a l i d e s a n d S u l f o n a t e s

DBU

* JOG,

47,

90%

1944 (1922)

DBN

60%

N a I , DMF

JOC,

47,

4352 (1932)

DBN o r DBU

95% JOC, -47, 4356 (1982)

- OLEFINS FROM HALIDES A N D SULFONATES

SECTION 205

Br

383

60% KOH/benzene

I

t

polyethylene glycol JOC,

Br Br

47,2493

80%

(1982)

Iron-graphi te

H

Bu JOC, -4 7 , 376 ( 1 9 8 2 )

Na2S*9 H20

Br

DMF

-0

S y n t h e s i s , 879 ( 1 9 8 1 )

Br

Z n , (H2N)*C=S

Synth Cornrn,

11,9 0 1

(1981)

769:

C O M P E N D I U M OF ORGANIC SYNTHETIC METHODS V O L 5

384

SECTION 205

Z n , TiC14 29%

TH F

Br

S y n t h e s i s , 1025 ( 1 9 3 2 )

C4H9

Br

NaSePh C H CH=CHC8HI7 8 17

Br Tetr L e t t ,

21,1877

(1980)

Tetr L e t t ,

3,3601

(1982)

95%

Br Br

H

CH3

a c t i v a t e d Ni

Ph

65%

2 Ph-CHBr2

Ph

Tetr L e t t , 23, 4215 (1932) c

SECTION 205

OLEFINS FROM HALIDES AND SULFONATES

385

c1

CHCl (C1Me2Si ) Pd(O)

c1

Ph Me

Chem Lett, 613 (1982)

\

/CHMqCi

1) PdC12L2 2) PhMgBr, NiC12L2

t

e

CH3CH Ph 1

Br

Me0

c1

SPh

JCS Chem Comm, 647 (1982)

I

@TMS,

Et3N

b

Pd(OAc)2, PPh3

Chem Lett, 1993 (1982)

Ph

70:;

COFIPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

386

/=\B( S i a)*

Bu

t

/=\ Hex

Br

SECTION 205

PdL4 Bu

NaOEt

49%

Tetr Lett, 22, 127 (1981) c

Review: "Pal ladium-Catalyzed Vinylation o f Organic Hal ides" 27, 345 ( 1 9 8 2 ) Grg React, -

Me 70%

Et Tetr Lett, -22, .959 (1981) Tetr Lett, 23, 1591 (1982)

SECTION 205

OLEFINS FROM HALIDES AND SULFONATES

@=c$

-

CuLi

t

PhS02CH=CHMe

2) Ht

Me Me-CH,

H/c=c,

3) Na-Hg

387

,Bu H

JCS Chem Comm, 523 (1981

PhMeCHF’gC’

-

.

chiral , polymer-bound ligand.NiC12

t

CH2=CHBr

H

k-cH=cH2 / Ph

93% 48% ee(S)

21, 4623 (1980) Tetr Lett, -

n-C5H1 lMgBr 2-

1 Me3Si CH2COOEt 2) H2S04/THF

+

CH2=C(!-C5Hl1

I2

78%

Tetr Lett, 23, 1035 (1982) 1 ) LiCHBr2

2) BuLi

n-C9H19-CH21 1)

Pr-CH21

+

n-C9H,9-CH=CH2 -

80%

PhCBr2Li

2) BuLi

w

Pr-CH=CH-Ph

74%

Comptes Rendus, 294, 37 (1982)

388

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 205

1 ) ClTMS

H, Me'

2, C=PPh3

I __1)

3) CSF 4) CeH17CH0

CH 3, &C=CH-C8H,

.8C%

21, 545 (1982) Angew Chen Int Ed, Section 206 Olefins from Hydrides

This section contains examples o f the conversion R-H conversions o f methylenes to olefins (R-CH2-R'

-f

tion 200.

+

R-C=C. For

R-C-R'), see SecII C

0 93%

JOC,

46,

4103 (1981)

SECTION 207

OLEFINS FROM KETONES

4,

389

1) PhSeCH2CH0

2 ) MeS02C1 Et3N JCS Chem Comm, 434 (1981)

n

C02Me

1) P hS02C: CS iMe 2 ) Ht 3 ) Me3SiCN

Section 2C7 Olefins from Ketones

0

FH2

J Chem Kesearch ( S ) , 24C (1982)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

390

0 1) LiCH2SPh II

SECTION 207

-

2) Imidazole-TMS &OH 3) LiN(i--Pr)2 4) KH Synthesis, 640 (1980)

Q u

78%

CH2-P( OE t)2 NaH, THF

+

w

15-crown-5

0 P h -C-CH3 I1

Ph, H HC='\p h

C6%

Synthesis , 117 (1981)

'

PPh3

RM

+

O

-c

2) H30+

CH20H

OTHP

85%

JOC,

9, 4260

(1900)

99% 2

SECTION 207

OLEFINS FROM KETONES

39 1

i-

35%

TeCr Lett, 21, 3621 (1980)

"Cycloalkenes by Intramolecular Wittig Reactions"

Review:

Tetrahedron, 36, 1717 (1980)

0

?2

II

C\ Pr 'gH1 7 0

CH2Br2-Zn TiC14, THF

'8'17

/c\

Pr

89%

Bull Chem SOC Japan, 53, 1698 (19%)

Ph2C0

+ BrCH2C-CH

-

0

1) Zn

2) HS

78%

Ph 10, 637 (1980) Synth Comm, -

392

COMPENDIUM

OF

O R G A N I C S Y N T H E T I C METHODS V O L 5

S E C T I O N 207

H

0 I

C-COOEt

t

0"

2 ) H30t

B u l l C h e m SOC Japan,

52,

3619 ( 1 9 7 9 )

1) C 1 2 T i C p 2

c5H11HH b

H

A 1 (L-Bu)~

C h e m L e t t , 429 (1982)

JOC,

47,

1983 ( 1 9 8 2 )

8 1%

SECTION 207

OLEFINS

1) NH,NHSO,Ar L

FROM

KETONES

L

Y

Org Syn,

b

$1,141

PhMgBr N i (acac)2

(1983)

-8

Tetr Lett,

OT f

Z e l a t e d methods:

v

Ph

OTMS

Q

393

1, 3915

7 37:

(1980)

Bu

Tetr Lett,

t

21,4313

(1980)

O l e f i n s f r o m Aldehydes ( S e c t i o n 1 9 9 )

394

COMPENDIUM OF OFGANIC SYNTHETIC METHODS VOL 5

SECTION 208

Section 208 Olefins from Nitriles

No additional examples Section 209 Olefins from Olefins Hx

HH Li

Et

t

'2

-

>=(, Et

I 1

G2%

Synthesis , 945 (1980)

h

OMe

Br

OMe

1) B u L i 2)

-

3) C13CCOOH 4) NaOAc, Ac20 5) TiC14, Ti (O-i-Pr)4

d=cH

Chem Lett, 591 (1980)

57%

SECTION 210

OLEFINS FROM MISCELLANEOUS COMPOUNDS

Ph-NH2, L-BuONO

395

7 8%

Pd (dba)

JOC,

5,4885

-

ti tanocene

(1981)

6

98%

Sy nt h es s, 53 (1982)

Review:

"The 1,5-Shift Reaction" Russ Chem Rev, 50, 666 (1981)

Section 210 Olefins from Miscellaneous Compounds

94%

Tetr Lett, 21, 945 (1380)

396

COMPENDIUM

OF

O R G A N I C S Y N T H E T I C METHODS VOL 5

S E C T I O N 210

60% Synth

Cornrn, -12, 813 (19Z2)

S y n t h Cornrn,

22,

813 (1982)

wSePh

Ph

+ BuMgBr Tetr Lett,

21, 87

(1980)

OLEFINS FROM MISCELLANEOUS COMPOUNDS

SECTION 210

elf"'

mo

Me3SiC1

Na I

3

:

SePh

39 7

JOC, 4 6 , 231 ( 1 9 8 1 ) c

use; a 1 ) H202

//

//

N - C- C H

H

2) A

II

82%

N-C-CH3 H

JCS Chem Comrn, 546 ( 1 9 3 1 )

L'

" '

Chem L e t t , 1209 ( 1 9 8 0 )

79%

398

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

n-C5H5Fe(CG)2CHCH2Hx Hx I

BF4 1) Ph3C00

2) NaI, acetone

+

SECTION 210

HxCH=CHHx

88%

JOC, 45, 291 (1980) Section 210A Protection o f Olefins Br2

Br

Or

&TeFla Synthesis, 1025 (1982) JOC, 47, 876 (1982) Tetr Lett, 23, 3601 (1982)

JCS Perkin I , 2520 (1981)

PROTECTION OF OLEFINS

SECTION 201A

399

R' R'

L/ electrochemical reducti

Tetr Lett,

22,

623 (1981)

Use of (diene)Fe(C0)3 complexes in the synthesis o f insect phero-

E configThe Fe(CO)3 complex locks the 1,3-diene in the uration, while other synthetic transfornations take place.

mones.

Cleaved by Et3N+0.

JCS Chem Conm, 373 (1981)

Compendium of Organic Synthetic Methods, Volume 5 Edited by Leroy G. Wade, Jr. Copyright 0 1984 by John Wiley & Sons, Inc.

CHAPTER 15 PREPARATION OF DIFUNCTIONAL COMPOUNDS Section 300 Acetylene - Acetylene No additional examples.

Section 301 Acetylene

-

Carboxylic Acid

I ( CH2 1 9COOH t

HMPA

b

Li Cz CH EDA

HCEC

( CH2 ) $OGH

05%

Synth Comm, 10, 653 (1980)

Section 302 Acetylene

-

Alcohol

0H 1) H2C=C=C B ' (OH) ' L (+)dial kyl'tartrate

-0 Ho

JACS, 104, 7667 (1962)

CH

H

56% 92% ee

SECTION 302

ACETYLENE

-

40 1

ALCOHOL

1) H2C=C=CHTMS, TiC14

C-C-H

2 ) KF, Me2S0

89% JOC, 45, 3925 ( 1 9 8 0 )

L i C-C-TMS Me20

-123'

\

80% ee

OH

Chem L e t t , 255 (1930)

C- C-CH

L i A1 H4

C-C-CH

Darvon a l c o h o l

45%

JOC, 45, 532 ( 1 9 8 0 ) Using a c h i r a l binaphthyl, T e t r L e t t ,

3

2, 247

(1981)

55% ee

402

COMPENDIUPI OF ORGANIC SYNTHETIC METHODS VOL 5

S E C T I O N 303

Section 303 Acetylene - Aldehyde Cii2-CH-CH(OEt I 2 Br Br I

I

00 Bu4N OH

H20/pentane

F

H-CEC-CH(OE~)~

67%

Ors Syn, 59, 10 (1980)

Section 304 Acetylene - Amide :do additional examples.

Section 305 Acetylene - Amine BrC H2C EC-CH2CH3

Ph2NH

NaOH/K2C03, PTC

* Ph2N-CH2C=C-CH2CH3

70%

JOC (USSR), 18, 848 (1982)

L DA

Hx-CH=CF2

Et20

Hx-C:C-N(i-PrI2 -

7 0%

Chem Lett, 935 (1580) 0

Ck!3(CH2)14C-C1 t

SnBu3

c

111

C NPh2

0

~

E-(CH2)14CH3 C C NPh2

88%

Ill

Liebigs Ann Chen, 1907 (1981)

SECTION 307

-

ACETYLENE

ETHER

403

Section 306 Acetylene - Ester

co

CjHl1-C-CH

PdC12, CuC12 KaOAc, NeOH

-

C5H,1-CiC-C02Me

a

74%

Tetr Lett, 21, 849 (1980) 0 I1

3

1) a-pinylborane

I1

Oct-C:C-CCH2CH2C-OMe

2 ) NaOH, MeOH

-

Oct-C:C

H

0

70-75% 85-93% ee 46, 4107 (1981) JOC, -

Section 307 Acetylene - Ether H2C=C=C0 I b e

THF/HMPT

+

( BuCuBr )MgC1 .Li Br

()Me

80%

JOC, 45, 1158 (1980)

oo Et-CrC-Li t

Bu-CH2-C!C-

1) THF

d i E C - E t 92%

2) CH31, THF/DMSO Synthesis, 459 (1981)

404

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

Section 308 Acetylene

-

SECTION 308

Halide

Synth Comrn, 10,345 (1980)

3u3P12

H-C?C-CH20H

HNPT

-

H-C-C-CH2 I

63%

Aust J Chem, 35, 517 (1982) Section 309 Acetylene - Ketone-

0 0 Ph-C-CH2-C-CH3 I1

I1

-

KF, Et2NCF2CHFCF3

0 Ph-C-C-C-CH3 II

72%

Chem Lett, 1327 (1S80) Ph-C-CH -I

0

CuI, it3N toluene

0 ,I

* Ph-CsC-C%

81%

II

%c-cl

Bull Acad USSR Chem, 30, 918 (1981)

SECTION 309 Ph-I

ACETYLENE

PdCl (dppf)

f

co

H-C-C-Ph

-

KETONE

405

0 I,

Ph-C-CiC-Ph

*

JCS Chem Comm, 333 (19811

0 Me2CH-C-C1

Bu3SnC:C-CH (OEt

I1

( Ph3P ) 2PdC 1

*

0 Ke2CH-C-C:C-CH(OEt)2 I!

73%

JOC, 47, 2549 (1982)

t

--"u"

AcB r

B u l l Acad USSR Chem, 29, 41C (19CO)

Bu-CsCA1Me2

1) Ni(acac)z DIBAL-H 2)

0""

-b

3) H300

JOC, 35, 3053 (19CO)

C-C-BU

70%

7 1%

406

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 309

0

&-c 1

cH ( c H

*

t

SnBu3

0

t- ( c H ~ ,) 4 ~ ~ 3

88%

111

C

I

C

I

NPh2

Ill

NPh2

Liebigs Ann Chem, 1907 (1981)

Section 313 Acetylene - Nitrile CN I C 111 C

Li I

C

111

r

PhOCN

92%

Synthesis , 150 (1980)

SECTION 3 1 1

S e c t i o n 311 A c e t y l e n e

-

ACETYLENE

407

OLEFIN

- Olefin 0

OP ( OPh)

PhC-C-A1 E t

2 w

0 c= c

Ph

70%

Tetr Lett, 21, 2 5 3 1 ( 1 9 8 0

1) CuBroSMe2

Bu

93%

2 ) Br-C-C-Bu

\

JOC, $6, 645 ( 1 9 0 1 )

C5H ll-C-CLi

TH F

+ L iI

-

CzC-BU

C5H l l - C ~ C

75%

Chem L e t t , 6 6 9 ( 1 9 0 0 )

408

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

(*

2 ) Et3A1 t

3 EtO-CFCH

4)

-

SECTION 311

80%

HC-C

S y n t h e s i s , 904 (1930)

L i- C- C-CH L i

I

JOC, 46, 5041 (1981) c

83%

Angew Chem I n t Ed,

1, 286

(1982)

CARBOXYLIC A C I D

SECTION 312

-

CARBOXYLIC A C I D

1) TMS-C-C PdL4,

409

ZnCl P

THF

2 ) KF, DMF

JACS, 102, 3298 ( 1 9 8 0 )

t

* 2) Fe(NO3).9 H20

TY2

Tetr Lett,

S e c t i o n 312 C a r b o x y l i c A c i d

- Carboxylic Acid

Mt-BuOOH o(acac)2

(YOTMS

1, 1595

-

(1920)

c:::!

T e t r L e t t , -22, 2595 ( 1 9 8 1 )

8600

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

410

LiCH-COOLi Bu

*

t

2) H30+

Br-CH-COOLi

SECTION 312

Et HOOC-CH-~H-C~OH

63%

I

Bu

Et

Synthesis, 710 (1980)

0 Cl-C-(CH2),-C-C1 0 I1

II

1) Meldrum's acid, DMAP 2) NaCNBH3, HOAc/THF 3) HC1, heat

0 0 HO-C-(CH2)n+4-C-OH $1

+

I1

.50% overall

Synth Comm, 12, 19 (1982) Section 313 Carboxvlic Acid - Alcohol

Ph-CH2COOMe

1 ) PhI(OAcI2 2) KOH, H20 3) H+

+

Ph-CH-C!IOH OH I

Tetr Lett, 22, 2747 (1981)

50 %

SECTION 313

CARBOXYLIC ACID

-

ALCOHOL

411

Chem L e t t , 569 ( 1 9 8 2 )

Ph

0

Ph

1) PrMgBr

2 ) H30

e

t

Pr, Ph'

C

/

OH

'COOH

62%

JOC, 4 5 , 2785 ( 1 9 8 0 )

Li I

CH-COOL1

1) I- i

LH-LUUt --- I ^"

2 ) H30t 57%

H

-

JOC, 4 5 , 447 ( 1 9 8 0 )

PhCHO t

1) Z n , THF

88%

Br Bull SOC Chim F r a n c e 11, 145 ( 1 9 8 0 )

412

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

Section 314 Carboxylic Acid

-

SECTION 315

Aldehyde

No additional examples. Section 315 Carboxylic Acid - Amide

J3C, 45, 5187 1980) Chem Ber, 113, 2323 1980) JACS, 102, 988 ( 1980 JACS, 103, 2273 (1981) 46, 2954 and 2963 (1981 ) JOC, Synthesis, 75 (1981) Related methods:

Section 316 (Acid-Amine); Section 344 (AmideEster); Section 351 (Amine - Ester)

Section 316 Carboxylic Acid - Aaine

H Y

c2' 0 '

H3C

(COO0)

chiral Co(II1) complex

NH2 H3C-C;;i-C000 88% yield (35% ee

JACS, __ 103, 21159 (Isel)

SECTION 316

CARBOXYLIC ACID

-

AMINE

413

COOH Me 0

P hCH2B r

2 ) H30t

H2N

%60% 91% e e 20, 798 (1981) Angew Chem I n t Ed, (S)-pyradoxami ne analog 7 - C O0 O H

Zntt

'

YH2

+

H III~C

Fle2CH

'COOH 6 3%

96% e e CIiem L e t t , 1765 and 1769 (1982)

1)

H2N-CH 2-CsCH

2 ) s i m i l a r , using

BzBr

B*xc COOH

H2N

63% 84% e e

3 ) CH3I 4 ) several steps Angew Chem I n t E d ,

19, 725

(1980)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

414

J3

CH,

ru

CH3CH2

C1 NH

'

EOC'

SECTION 316

H

t

COOH

Tetrahedron, 36, 2961 (1980)

Xelated methods: Section 315 (Acid-Anide); Section 344 (AmideEster); Section 351 (Amine-Ester) Section 317 Carboxylic Acid - Ester No additional examples.

Section 318 Carboxylic Acid

-

Ether, Epoxide

No additional examples. Section 319 Carboxylic Acid - Alkyl Halide 0 11

Ph-C-NH(CH2)5COOH

C12, 02, C1S03H C1CH2CH2C1

+

0 c1 Ph-E-NH(CH214-bHC00:i 48-52%

SECTION 319

CARBOXYLIC ACID

-

-t

ALKYL HALIDE

415

F

CH-COOE t

1) LDA, Me3SiC1 2 ) CF30F

85%

3 ) H20

JACS,

102, 4 3 4 5

(1980)

S y n t h e s i s , 963 ( 1 9 2 2 )

0 I1

c13c-c-c1

/\/\/\//

RuCl 2 L 3

0 II

c-c1

1

Chem L e t t , 1 2 5 5 ( 1 9 8 2 )

93%

416

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

S e c t i o n 320 C a r b o x y l i c A c i d

-

SECTION 320

Ketone

Mo ( a c a c )

go?;

t-BuOOH CH3

22, 2595 (1981) T e t r L e t t , --

Li

1) PhiHCOOLi COOH

2 ) H30t

QO2

727;

Chem L e t t , 1505 (1982)

4 M gB r

S i P h 2Me

1) 2 ) Jones ox.

-

O F

COOH

Tetr Lett, 23, 271 (1982)

50%

SECTION 3 2 1

CARBOXYLIC A C I D

-

NITRILE

417

n

S y n t h e s i s , 74 ( 1 9 8 1 ) Also v i a :

Ketoesters (Section 360)

S e c t i o n 321 C a r b o x y l i c A c i d

‘I

- Nitrile

C uO/ NH 3 1 1r e a g en t

p.yri d i ne

OH

60-707; JOC, 45, 2737 ( 1 9 8 0 )

0 II

C7H, 5 - C - I

CuCN

0 II

+

C7H15C-CN

78%

Angew Chem I n t Ed, 21, 83 ( 1 9 8 2 ) c

418

COMPENDIUM OF ORGANIC SYNTHETIC FIETHODS VOL 5

SECTION 321

0

B u 3S n CII

9 2%

ACN

Tetr Lett, 21, 2959 (1980)

CO, KCN

Ph-I

PhPdIL2

0 I1

33%

PhC-CN

B u l l Chem Soc Japan,

'1 'J

Ph-C-CH2Br

Review:

(1981)

NH,

Ph-C-CHO or

2, 6 3 7

Ph

*

0 11

Ph-C-CN

9 7%

S y n t h e s i s , 844 (1980)

"The C h e m i s t r y o f A c y l Cyanides" 21, 35 ( 1 9 3 2 ) Angew CIiem I n t E d , -

Also via:

S e c t i o n 361 ( C y a n o e s t e r s )

CARBOXYLIC A C I D

SECTION 322

-

OLEFIN

4 19

- Clefin

S e c t i o n 322 C a r b o x y l i c A c i d

0

I1 (Me0)2PH, NaOMe

Ph

Ph-CHO

89% C1 CH2COOH , MeOH

JOC,

CH2=CH-COOH t

COOH

46,

H2PtC1

2514 ( 1 9 8 1 )

*

Ph-CH=CH-COOH 86%

CH3COOH

Ph4Sn

B u l l Acad USSR Chern,

4

CHO

(1982)

s o d i urn c h l o r i t e NaH2P04 ,

COOH

t-BUOH H20/ -

Tetrahedron ,

0 I1 TMS-CH2-C-TMS

3,2211

90%

37,

2091 ( 1931)

- AcooH

1) LDA, Me1

2) LDA, BuCHO 3 ) Hf

~70%

Bu

JACS, 103. 6217 ( 1 9 8 1 )

14 e

420

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 322

1) O=C( COOEt)2

COOH

%62%

2) I04B 102, 2473 ( 1 9 8 0 ) JACS, -

bo2 0

ba;

aR--0

*

R-CH=CH- ( C H ~2~~~~ )

(R = lo a l k y l ) Chem B e r ,

6==x uMg

go

114,909

(1981)

* v Bu

2 ) H30t

907;

H

66%

Chem L e t t , 1123 ( 1 9 8 0 )

1) BuMgBr, Co12

2 ) H3Ot

COOH

+

L

C

O

O

Bu

B u l l Chem SOC J a p a n ,

55,

3555 ( 1 9 8 2 )

CARBOXYLIC ACID

SECTION 3 2 2

-

421

OLEFIN

OH Tetr Lett,

4

0

22,

94%

1817 ( 1 9 3 1 )

CUI

COOH

+

90% Tetr Lett,

23,

3583 ( 1 9 3 2 )

Tetr Lett, 23, 5 1 5 1 ( 1 9 8 2 )

422

COMPENDIUM

OF

ORGANIC SYNTHETIC METHODS

VOL 5

SECTION 322

P ~ ( O A C ) ~Na2S20G ,

co

C-Ph

I

C-Ph

II

I1

0

0 Chem L e t t , 1151 ( 1 9 8 2 )

Also v i a :

i l y d r o x y a c i d s ( S e c t i o n 3 1 3 ) ; O l e f i n i c amides ( S e c t i o n 349); O l e f i n i c e s t e r s ( S e c t i o n 362); O l e f i n i c n i t r i l e s ( S e c t ion 376 )

S e c t i o n 323 A l c o h o l

- Alcohol Ph

1) oso4

Ph

d i h y d r o q u i n i ne a c e t a t e

*

2 ) LiA1H4

90%

HO H#oH

83% ee

Ph Ph JACS,

202,

4263 ( 1 9 8 0 ) H

H

Os04/Et3N0 p y r i d i ne

OH

CH2CH20MEM Tetr Lett,

22, 449 ( 1 9 8 0 )

ALCOHOL - ALCOHOL

SECTION 323

x

Ph2Se0

-

Os04 ( c a t . )

42 3

1

I

OH

OH

98%

Tetr L e t t , -22, 2051 (1981)

Review:

"Osmium Tetroxide Cis-Hydroxylation of Unsaturated Substrates" Chem Rev, -80, 187 (1980)

0

1) NBS, H20 2 ) N C C H 2 C O O H , TsOH 3 ) NaH

aoH OH

Tetr L e t t ,

23, 4217

(1982)

Synthesis, 230 (1981)

70%

424

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 323

2 ) NaOti H20/EtOH

OH

1) TlOAc

~60%

1 2 , HOAc 2 ) H20 3 ) NaOH H20/E t O H Org Syn,

55, 169 ( 1 9 8 0 )

0

JOC,

45,

1 (1930)

1) 2 BuLi

Tetrahedron,

3 , 299 ( 1 9 3 0 )

SECTION 3 2 3

2 Ph-CHO

ALCOHOL

-

ALCOHOL

OH OH

T i C 1 3 , NaOti

o r Fe(C0)5,

425

i1

pyridine

+

88%

Ph-C-C-Ph

i1

H H

Chem L e t t , 1 1 4 1 ( 1 9 8 0 )

23, 3 5 1 7

Tetr Lett,

(1982)

0

Ph-id-COOH

COOH I

T i C 1 3 , H20

t

P

Ph-C-C-CH I

OH

0

CH3 1

13

85%

OH

II

CH3-C-CH3

2

6

JOC, 47, 2 8 5 2 ( 1 9 8 2 )

Ce-I2 95%

Tetr Lett,

23,

1353 ( 1 9 8 2 )

BrMg( CH2)4MgBr

72%

JOC,

_45,_ 1828

(1980)

426

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 323

1) MCPBA

65%

2 ) LiA1H4

HO JACS,

Review:

104, 1769

"Advances i n S t e r e o c h e m i c a l C o n t r o l :

(1982)

The 1,2- and 1,3-

D i o l Systems" A l d r i c h i m i c a Acta, 15, 47 ( 1 9 8 2 )

mCH3 0 - S iMe

-t-B u

2 ) NaBH3CN

66%

OH

tNH2 Tetr Lett,

23,

1717 ( 1 9 6 2 ) ?H

OH

70%

O2 , p e r o x i dase

COOH

COOH

JACS, Also v i a :

103,6263

(1981)

H y d r o x y e s t e r s ( S e c t i o n 3 2 7 ) ; D i e s t e r s ( S e c t i o n 357)

ALCOHOL - A L D E H Y D E

SECTION 324

S e c t i o n 324 Alcohol

OH

-

427

Aldehyde RUC1 2 L 3

( CH2 ) p

benzene Tetr Lett,

22, 1605

o

(1981)

OH

n

T e t r L e t t , 2 2 , 4077 (1981) c

1) L - B u N H 2

( p r o t e c t s t h e a1 dehyde)

2 ) Li

0

H c

(L-BuO)?Al

H

43 )) Hb a2 s0 i c a1 umi na

Tetrahedron,

c

CHO

I

g,1327

( 1982)

C9%

428

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

Review:

SECTION 324

"The D i r e c t e d Aldol Reaction"

Org React,

Related methods:

Alcohol

S e c t i o n 325 Alcohol

-

-

21, 203 (1982)

Ketone ( S e c t i o n 33)

Amide

0 II EtOCNClNa, OsOa

-+HNCOOEt

OH

78%

JOC, 4 5 , 2710 (1980) L

1%0sO4, TsiiCliia

CHCl 3/H20, P .T, C

..SO%

. NHTs

Org Syn,

61,

85 (1983)

SECTION 326

ALCOHOL - AMINE

429

1) 2 BuLi

NHL-Bu

Ph2C 1 OH

2 ) Ph2C=0

88%

JOC, -45, 4257 (1980)

1) R C N , HBF4 2 ) NaOMe, MeOH

Tetr Lett,

Section 326 Alcohol

-

R

22,

341 (1901)

Arnine

Synthesis , 376 (1981)

430

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 326

To''e DME/

1) L-BuNOs03, p y r i d i n e

2) LiA1H4

JOC, 45, 2257 (19GO)

oo

A1 E t 2 I

74%

Tetr Lett,

1) Me3SiCN, Zn12 2 ) KF

Me

3 ) H C 1 , MeOH JACS,

Review:

22, 195

-

(1981)

aoH 6 3%

5

CH3 N H 2 .HC'I

jl, 5849 (1932)

" S t e r e o s e l e c t i v e S y n t h e s i s o f Diastereomeric Amino Alcohols from Chiral Aminocarbonyl Compounds by Reduction o r by Addition o f Organoinetall i c Reagents" S y n t h e s i s , 605 (1982)

SECTION 326

-

ALCOHOL

C5H 1CH=N02Si R3 t

Ph-CHO

A MI N E

-

431

C H 5 11,

2 ) LiA1H4

OH

CH-CH,

0

H2”

64% Ph

H e l v Chim A c t a , 64, 2264 ( 1 9 8 1 ) c

Bu

S y n t h e s i s , 270 ( 1 9 3 1 )

% H-C-N

1) L - B u L i 2 ) PhCHO 3 ) MeOH, H20 4 ) KOH, H20 JACS,

- ?YPh OH

102, 7125

5 7%

(1930) H - N,- 0 H

SnCl 2/HC1

S y n t h e s i s , 599 ( 1982)

90%

C O M P E N D I U M OF ORGANIC SYNTHETIC METHODS VOL 5

432

SECTION 327

S e c t i o n 327 Alcohol - E s t e r

E tOAc OH

P

n e u t r a l a1 urni na

S y n t h e s i s , 789 (1981) T e t r L e t t , 22, 5003 a n d 5007 (1981)

AcO

OH

OH

-4w

w

Cs F

Chern Lett, 563 (1981)

SECTION 327

Q

ALCOHOL

-

ESTER

433

-$ CH20Ac

CH20H

B F Ac20 3*E t20

OH

0 I1

Ph-C-COOEt

63%

OH Chem ?harm B u l l , -29, 3202 ( 1 9 3 1 )

chiral dihydropyridine

*

OH I

?h-CH-COOEt

JACS, 103, 2091 ( 1 9 8 1 ) JACS, l OJ,

4613 ( 1 9 8 1 )

Tetr Lett,

23,

4585 (1982)

80% 93% e e

434

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

&‘y

SECTION 327

1) n-C5H11CH0

OLi

+

2 ) H20

CH 3

JOC, 34, 1727 (1920)

Br I

Ph-CH-C02Et t

Ph-CHO

1) Sn

2 ) H20

C02Et I Ph-CH-CH-Ph I OH

95%

G O : 20 e r y t h r o : t h r e o

Chem L e t t , 161 (1982)

Synth Comm,

Also v i a :

Hydroxyacids ( S e c t i o n 313)

11,505

(1981)

ALCOHOL - E T H E R , EPOXIDE

SECTION 328

S e c t i o n 328 A l c o h o l

iH

-

435

E t h e r , Epoxide

PBu

1) NaOH, H20

(OH

70% 2) BuCl

LOH JOC,

$5,1095

(1930)

LiAl H 4 benzene

0 Me

OMe

bH

O 1.1e

uoH

JCS Chem Cornrn, 507 (1930)

Nafion-H

74%

MeOH/ether

S y n t h e s i s , 280 (1931)

/ '

OMe

436

COMPENCIUM OF ORGANIC SYNTHETIC METHODS VOL 5

c:\

Jp

1) PhCHO,B-Cl 2)

Ph

OMe

95%

OMe JOC,

5,2498

Tetr Lett,

H O J - (

SECTION 328

KHS05, acetone

(1902)

2, 1657

(1920)

oJ( - ( P

18-crown-6, CH2C12/H20 JOC,

47,

9 1%

2670 (1982)

Ti ( OCHMe2)4, CH2C1

HO+

L(t)diethyl Me 3C- OOH tartrate

JACS,

102, 5974

77% 95% ee (1900)

SECTION 328

ALCOHOL - E T H E R , EPOXIDE

43 7

-

OH NaBH4, Ce

c

3+

85%

MeOH

98% t r a n s Synth Comrn,

10,623

(1930)

83% 99% e r y t h r o Tetr Lett,

22,

4723 (1931)

Amberlyst A26('0H)

--

I

CH30H

* JOC,

47,

(TOH

4626 (1982)

90%

COMPENDIUM

438

OF O R G A N I C SYNTHETIC METHODS VOL 5

S e c t i o n 329 A l c o h o l

1)

-

SECTION 329

Halide c1

T s - b Naa 625

2 ) H30'/acetone

OH S y n t h e s i s , 362 ( 1 9 0 1 ) Ph

Ph

p\

toH

H20/ DMSO

Ph

Org Syn,

MeOOC

MeOOC

59,

16 (1980) MeOOC

electrolysis NaBr , H2S04 , H20/MeCN

72% MeOOC

5, 3312

tHO JOC,

OH

(1981)

cathodic reduction CC14, CHC13, DMF

T e t r L e t t . 23. 1609 ( 1 9 8 2 )

62%

SECTION 330

ALCOHOL

-

4 39

KETONE

H

75%

CHC13 o r p y r i d i n e

OH

11,227

S y n t h Cornm,

(1931)

-

Cr02F2

AcO

JCS P e r k i n

S e c t i o n 330 A l c o h o l

-

OH

F

I , 639 ( 1 9 8 0 )

Ketone

0

4,

NaBr03

OH

OH Tetr Lett,

_23, 539

(1982)

COMPENDIUM

440

OF

O R G A N I C SYNTHETIC METHODS VOL 5

O*H

NaOC1, HOAc

Tetr Lett,

S E C T I O N 330

OH*

3,4647

85%

(1982)

N i (OH)2 e l e c t r o d e

u, +

HO

vnu

n..nii

Tetrahedron ,

3,3299

-

( 1982)

1) M e 3 S i I , HMDS 2 ) 0sO4, NMMO Ph

3 ) H20

Tetr Lett,

0 II

Ph-C-CH3

PhI=O

CH30H

2, 607

OH

I1

w

60%

Ph-C-CH20H

Tetr Lett,

22,

9 8%

(1981)

0

o r PhI(OAc)2 -OH,

Ph

1283 ( 1 9 8 1 )

SECTION 330

ALCOHOL

441

- KETONE

76% Tetr Lett,

microbial reduction

~

23,

2917 ( 1 9 8 2 )

&H'H3C'/

60%

JOC, _ 4.7, -2820 ( 1 9 8 2 )

14e

CH

- C-Me

1) e t h e r

2) H30t t

3 ) HgO, BF3.Et20

-

Me

) ,

Ph-MgBr

OH

CH2-C-Me I

Ph

60%

.?i

S y n t h e s i s , 561 (1980)

442

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 5

JOC,

C-CH

47,4 0 2 4

1) PhHgOH, CHC13

~

SECTION 330

(1982)

&-CH3

0'

4 7 , 3331 ( 1 9 8 2 ) JOC, 0 Ph

Do

1) ( Et0)2bl-h-OTMS 2 ) H0 T e t r Lett,

8

NMe 1) E t - 6 - L i CN

2 ) H30'

i-Ph

11,1017

83%

(1930)

'6

E t 72%

Chem L e t t , 7 1 ( 1 9 8 0 )

SECTION 330

ALCOHOL

- KETONE

44 3

U

CuBr, THF PhCHO

B u l l Chem S O C J a p a n , -53, 3 3 0 1 (1980)

0 OTMS

1) ( Et2N)3SB T M S F F

+ 2)

67%

CHO

(100% e r y t h r o )

3 ) H20

JACS, 103, 2106 ( 1 9 8 1 ) ~

i-Pr2NLi

0

Ph

90%

E t 3 B , THF 2 ) PhCHO Threo product i s favored by a 97/3 r a t i o . Tetr Lett,

23,

2387 ( 1 9 8 2 )

Chem L e t t , 509 ( 1 9 3 2 ) Chem L e t t , 1 2 9 1 ( 1 9 8 2 )

444

COMPENDIUM

OF O R G A N I C SYNTHETIC METHODS VOL 5

B u l l Chem SOC Japan,

SECTION 330

53, 174

(19GO)

A l d o l r e a c t i o n s o f boron e n o l a t e s w i t h aldehydes t o f o r m e r y t h r o JACS, 102, 4548 JACS, 103, 1566 2127 JACS, JACS, 3099 3229 JACS,

a1 coho1 s :

?im, my

z,

1980) 1981) 1981) 1981) 1981)

Using Z r enolates: JACS,

103,2876

(1981)

Erythro o r threo selectivity: JACS, 103, 4278 ( 1 9 8 1 ) * .

0 Ph+Br

1

1) Sn, DMF/CH2C12

t

2 ) H20

* Ph

a 1

TO,

99%

92:8 e r y t h r o : t h r e o CHo Me Chem L e t t , 467 ( 1 9 8 2 )

ALCOHOL - KETONE

SECTION 330

-

OSnE t3 PhCHO

W

445

P

h

32%

JCS Chem Comm, 162 ( 1 9 3 1 )

Tetr Lett,

1) Sn(OTfI2

0 I1

Ph-C- CH2CH

23,

627 (19C2)

CN-Et

2) i-PrCHO

V

*

3) H20

j

-

P

r

30%

Ph CH3

91:9 e r y t h r o : t h r e o Chem L e t t , 353 ( 1 9 8 2 )

1) S n ( O T f ) 2

0 II

Ph-C-CH2CH3

CN-Et 78%

Chem L e t t , 1 4 4 1 (1982) Chem L e t t , 1459 (1932)

446

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 330

3) s i l i c a gel Tetr Lett,

2,3 6 1

(1980)

B u l l Chem S O C Japan, -_ 54, 274 ( 1 9 8 1 )

6

($

1) C l T i 6 - o 3

Ph

2 ) PhCHO

36% e r y t h r o

Tetr Lett,

6 Hgl

2,4 6 9 1

0

PhCHO

*

BF3*0Et2

(1981)

OH

"

W

P

h 85% 80% e r y t h r o

JACS, 104, 2323 ( 1 9 8 2 )

Review:

"The D i r e c t e d A1 do1 R e a c t i o n " Org React, -28, 203 ( 1 9 3 2 )

SECTION 330

CH3CH=C,

ALCOHOL

-

KETONE

447

,Et OZrCl Cp2

+

2 ) H20

Ph-CHO

Ph

VEt CH3 90%

Tetr Lett,

21,

83% e r y t h r o 4607 (1980)

64%

JACS,

2, 1777

0"

o"li

+

TH L DAF

NC

(1982)

-Yo-EE /I (EE

=

ethoxyethyl) JOC,

45,

395 (1980)

72%

448

COMPENDIUM

OF

ORGANIC SYNTHETIC METHODS VOL 5

3) H20 Tetrahedron,

Raney N i

,

37, 3 9 9 7

(1981)

OH

HC1 Me

MeOH, H20

-

SECTION 330

H

9 5%

Me

c

Me Tetr Lett,

0-

c 5 H ’ 1 4 &

N

1) 2 - B u L i

2)

3, 3 1 2 3

c

5

(1922)

H

@o

1

u

OH

Tetr Lett,

22,

3699 ( 1 9 8 1 )

0

CH2(COSEt)2, DABCO

75%

2 ) Raney N i

CH2CH20H Can J Chem,

60,

94 ( 1 9 8 2 )

SECTION 331

ALCOHOL

S e c t i o n 331 Alcohol

-

-

NITRILE

449

Nitrile

1) Me3SiCN,

Zn12

Ph,C=O L

Ph C/OH 'CN

2 ) H30t, THF

Org Syn, _6 0 , 14 ( 1 9 8 1 )

'YCN 3) NH4C1

10, 49 ( 1 9 8 0 ) Synth Comm, --

CH3CH2CN Bu2BOTf

t

-i-Pr2NEt

w

FH

3 Ph-CH-CH-CN

Ph-CHO

9 0%

I

OH

Chem L e t t , 1401 ( 1 9 8 2 )

0 I1

NrC-CH2-C-SBz

1) NaH, i - B u X

2 ) NaH, PhCH2X

i-Bu -/ N!C-C-CH20H 1

3) NaBH4

CH2Ph

Tetr L e t t ,

23,

3151 (1982)

76%

450

COMPENDIUM

OF

S e c t i o n 332 A l c o h o l

O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 332

- Olefin

A l l y l i c and b e n z y l i c h y d r o x y l a t i o n (C=C-CH

-f

C=C-C-OH,

etc.) i s

l i s t e d i n S e c t i o n 4 1 ( A l c o h o l s a n d Phenols f r o m H y d r i d e s ) .

( Ph3P)2CuBH4

o r (Et0)2SiHMe, mCii0 -

Ph

{5

KF

CH OH

-2

c-

Ph

99%

JCS Chem Comm, 121 ( 1 9 3 1 ) Tetr Lett,

22,

675 ( 1 9 3 1 )

Reagent

Reagent

Reference

(j-Bu) 3Al

Ph2SiH2, L3RhC1

_47, 4640 ( 1 9 2 2 ) O r g a n o m e t a l l i c s , -1, 1390 ( 1 9 8 2 )

NaBH4-CeC1

JACS,

t-BUNH2'BH3

Tetr Lett,

ZnBH4 ( e r y t h r o p r o d u c t )

21, 1641 (1980) Tetr Lett, -

L i A1 H4 , !-methyl

JCS Chem Comm, 1026 ( 1 9 8 0 )

ephedrine

( o p t i c a l l y a c t i v e product)

( i-Bu)2Al-0

JOC,

103, 5454

(1981)

21, 693

and 697 ( 1 9 8 0 )

Chem L e t t , 9 8 1 ( 1 9 8 0 ) B u l l Chem SOC Japan,

54,

3033 (1981)

( g i v e s s t e r e o s e l e c t i v i t y i n r e a c t i o n w i t h PG i n t e r m e d i a t e )

SECTION 332

-

ALCOHOL

OLEFIN

45 1

1) M e 3 S i I

8 1% 2 ) DBU o r DBN 3 ) H30t Tetr Lett, JOC,

O

‘gH17

f

45,

3,2329

(1980)

924 and 2579 (1980)

*

i

PdL4 OH

Tetr Lett, Bu-Li

+

Et 3 N

-

2,2575

(1981)

BuAOH 79% 94% 2

Tetr Lett,

2,577

(1981)

452

COMPENDIUM

OF O R G A N I C SYNTHETIC METHODS VOL 5 1) Ph3P=CHLi ~

1) Me3A1, Cp2ZrC12 2) B u L i 3,

'i

H' JACS,

Hx-C-CH

voH #'

2) Ph-CHO

4

SECTION 332

c=c

104,4724 Hx

Me

6 5%

/H

'Ph

(1952)

x"

a 7%

CH2CHOH I

CH3

S y n t h e s i s , 1034 ( 1 9 8 0 )

H-CEC

Y ,, ,

'OAc

+ Ph

JACS,

2, 2330

70% 60% ee (1982)

SECTION 332

-

ALCOHOL

1) DIBAL-H

2 ) Ph3P=CH2

OLEFIN

453

-EO 55%

3 ) Ht

S y n t h e s i s , 1015 ( 1 9 3 0 )

Cp2Ti

:2

0 II

1) CH3-C-CH=CH2

91% 2 ) HC1

H3

Tetr Lett,

7 SiMe3

Ph

CH3CH0

22,

-

TiC14, CH2C12

H

243 (1931)

--

OH

Ph

CH3

76% 86% ee

mCH

JACS, 104, 4963 ( 1 9 8 2 )

OCH2 Me2A1 CH3CH0 C1

9 1%

Tetr Lett, JACS,

21,

104,555

1815 ( 1 9 8 0 ) (1932)

454

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

dK

ZnCl*

I

-

SECTION 332

OH

xyl ene

c1

S y n t h e s i s , 310 (1981)

k Bu

Bu2B

t

Chem L e t t , 993 (1980)

1) S n , THF t

2 ) H20

OH

-A Ph

CHO

n Ph

Chern L e t t , 1507 (1980)

Chem L e t t , 1527 (1981)

\87%

S E C T I O N 332

ALCOHOL

-

OLEFIN

455 Me

OH

Me CHO

OH

H e l v C h i m Acta,

$5, 1258 (1982)

MgCl CH,

+ OH

Cp2ZrC1 Tetr Lett,

_22, 2895

T e t r Lett,

23,

90% 88% t h r e o (1931)

3497 (1932)

456

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 332

s-Bu)~BH L i (72% MeLi

T e t r a h e d r o n , 37, 3943 ( 1 9 8 1 ) c

0

1) LiCH2SPh I1

&OH

2 ) Irni d a z o l e - T M

w

3) LiN(i--Pr)2 4 ) KH

78%

v

S y n t h e s i s , 640 (1980)

C H -C-C-CH2Br 5 11 t

CrCl

-

0

?sHll

H2C=C=C

7 8%

HO Tetrahedron,

2,1359

OH

z n ( Cu) HC- C

(1931)

>95%

MeOH, A

Tetr Lett,

2,1069

(1980)

ALDEHYDE

SECTION 335

Also v i a :

-

AMINE

457

Acetylenes - Alcohols ( S e c t i o n 302)

S e c t i o n 333 Aldehyde

mOH

-

Aldehyde

polymer-bound p e r i o d a t e 90%

JCS Perkin I , 509 (1982)

1) 03, R O H , TsOH 2 ) Me2S, NaHC03

-C HO

CH ( OR)

*

T e t r L e t t , 23, 3867 (1982) c

S e c t i o n 334 Aldehyde

-

Amide

No a d d i t i o n a l examples.

S e c t i o n 335 Aldehyde

-

No a d d i t i o n a l examples.

Amine

9 3%

458

COMPENDIUM

OF

O R G A N I C SYNTHETIC METHODS VOL 5

S e c t i o n 336 A l d e h y d e

-

SECTION 336

Ester

96%

Tetr Lett,

S e c t i o n 337 Aldehyde

-

3,3867

(1922)

Ether, Epoxide

No a d d i t i o n a l examples.

S e c t i o n 338 A l d e h y d e

- Halide

A m b e r l y s t A-26 ( I C 1 2 q

-cHo cc1

*

YC

JCS Chem Comm, 1278 ( 1 9 3 0 )

c1

84%

SECTION 338

ALDEHYDE

-

459

HALIDE

A c t a Chem Scand B y

34,

4 7 (1920)

Bu-CBr2Li t

2 ) H30t

0 I1

H- C- OMe

*

May a l s o be used t o f o r m a-monohalo a l d e h y d e s . Synthesis

C- CH

78%

Bu-CBr2-CH0

644 (1980)

hHO

1

1) 12

-

2 ) p y r i d i n i u m dichromate

Tetr Lett,

66%

ZZ, 1041 (1981)

460

COMPENDIUM

OF ORGANIC

S e c t i o n 339 Aldehyde

-

SYNTHETIC METHODS VOL 5

SECTION 339

Ketone

croH Ph

p y r i d i n i urn c h 1o r o c h rorna t e 70%

OH

22,

S y n t h Comm,

0

1) 03, MeOH

MeOH

-5

Tetrahedron,

$,

3013 ( 1 9 3 2 )

CH (OMe)

CH (OCH3) BF3

872

T e t r L e t t , 23, 3595 (1922) c

0 I1

c 1 3c-c-c1

H2C=CHOEt

77%

2 ) (NH2)2C=S

6 t

333 ( 1 9 8 2 )

Et3N

Et O H

-

0

OEt 1

I1

C13C

A.

CH, CH2

Chern B e r ,

92%

OE t

215, 2766

(1922)

SECTION 339

ALDEHYDE

(11

06

-

KETONE

461

CH( O E t ) 2

1) SnC14

90%

CH( OEt) 2 ) H20

Chem L e t t , 1307 ( 1 9 8 2 )

-

1) PhSeTMS, TMSOTf

CH (OE t ) 2

2 ) HC(OEt)3, TMSOTf 3 ) H202

Tetr Lett,

76%

22,

1E09 ( 1 9 8 1 )

0

100% S y n t h e s i s , 245 ( 1930)

462

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

-

S e c t i o n 340 Aldehyde

SECTION 340

Nitrile 1) Nati, t-BuOH

CH2N02 CN

2 ) KMn04 3 ) Na2S2C5,

81%

H2S04

CN

JOC,

47, 4534

(1982)

S e c t i o n 341 Aldehyde - O l e f i n For the o x i d a t i o n o f a l l y l i c a l c o h o l s t o o l e f i n i c aldehydes s e e a l s o S e c t i o n 48 (Aldehydes from A l c o h o l s ) .

2 ) NaI04

9 0% Tetr Lett,

JOC,

46,

3,2105

2920 (1931)

(1982)

S E C T I O N 341

H C=C=C,

,OFle

2

TMS

ALDEHYDE

-

OLEFIN

463

1) BuLi 2 ) BuBr

Bu

3 ) Bu N F 4Q 4) H 3 0

W

Tetr L e t t ,

JOC,

C

3,3937

35,1061

H

O

(1980)

(1981)

PhMgBr

*

t

E to-CH=C- CHO

52%

Ph-CH=C-CHO

CH3

I

CH3

Angew Chem I n t E d ,

19,816

(1980)

464

SECTION 341

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

0

3) DBU, E t 2 0 JOC,

2 ) Ht t

50%

S y n t h e s i s , 137 ( 1 9 8 1 )

1) PdCl,, Me0

(1982)

1) r n o n t m o r i l l o n i t e clay

t

@OE

47,5017

AcOH

L

NaOAc

2 ) Ph-CH=CH2

Tetr Lett,

Meo

rP

3, 1957

HO

(1982)

81%

SECTION 341

-

ALDEHYDE

Hb

OLEFIN

1) PhSCl, E t 3 N

C - C-TMS

2 ) H20 3 ) AgN03, H20/MeCN

b

Tetr Lett,

465

6'; 2, 2021

6&%

(19E1)

Chem L e t t , 1997 ( 1 9 2 2 )

1) H202, CH30H CH2 NMe

2 ) Ac20

60%

Chem L e t t , 1927 ( 1 9 8 2 )

0

1) Me,S=CH, L

L

-I

He1 v Chin1 A c t a ,

Also via:

3 - H y d r o x y a l d e h y d e s ( S e c t i o n 324)

IT

- w

$3, 1665

- CHO

(1980)

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

466

Section 342 Amide

Y

-

SECTION 342

Amide

P h N C , TiC14 b

NCH\

HN

OMe HN COOMe I

’ ‘CNHPh CH

0

I

COOMe Tetr Lett,

in i NS X S NH2

22,

82%

2411 (1981)

0

I

c-

N

0

H

H

I

II

Chem L e t t , 159 (1980)

Indian J Chem, l 9J,

70 (1980)

AMIDE

SECTION 342

-

AMIDE

46 7

c1 I

P h - C=NMe t

0

I1

NaOH, H20 CH2C12, Bu N B r

Ph- COOH

*

Ph-C,

80%

NMe

Ph-C’

I1

0

4Qk3

S y n t h e s i s , 114 ( 1 9 8 0 )

0 II

H3C-C-N( CH0)2

75%

c ,H x O

CHO

S y n t h e s i s , 264 ( 1 9 8 2 )

0 11

1) 120°

Me

0 11

$-NH- C-Me

7 N02 S y n t h e s i s , 119 ( 1 9 8 0 )

Also via:

D i c a r b o x y l i c a c i d s ( S e c t i o n 312); Diamines ( S e c t i o n 350)

468

COMPENDIUM

OF

S e c t i o n 343 Amide

O R G A N I C SYNTHETIC METHODS VOL 5

-

SECTION 343

Amine

A

0

0

0-NH

I,

I1

S y n t h e s i s , 1092 ( 1 9 8 2 )

S e c t i o n 344 Amide

-

Ester

-x

COOMe

Ac20/AcOH

( Re2S,)

N (COMe)

N3

Angew Chem I n t Ed,

0 I,

,C-Ph

HN,

CH ( COOE t )

1) B r 2

4 ) H30'

3,203

(1982)

0 II

2) H u n i g ' s base 3) B u L i

93%

,C-Ph +

HN,

66%

C( COOE t ) 2 I

Bu Angew Chem I n t Ed,

21, 203

(1902)

A M I D E - ETHER

SECTION 345

0

F C H O

bl(OEt)* Z-NH-CH-COOEt

B0

469

"., A *

h

Z-NH-C-COOEt

80%

21, 776 ( 1 9 8 2 ) h g e w Chem I n t i d , -

GH

Me0

O'Et

77%

JOC,

R e l a t e d methods:

45,

4519 ( 1980)

S e c t i o n 315 ( A c i d - A m i d e ) ; S e c t i o n 316 ( A c i d Amine); S e c t i o n 351 ( A m i n e - E s t e r )

S e c t i o n 345 Amide

-

Ether

S y n t h e s i s , 315 (19DO)

470

COMPENDIUM

OF

ORGANIC SYNTHETIC METHODS VOL 5

0

SECTION 345

0

UN-P-N i K0

0

Ph-0-CH2COOH

U I U

c1

Ph-o-Ck92%

aNH2aNH t

[=O

CH3

CH 3

S y n t h e s i s , 547 (19GO) S e c t i o n 346 Amide

-

Halide

No a d d i t i o n a l examples.

S e c t i o n 347 Amide

)-

C- C- NMe

-

Ketone

Ph-I=O

44%

C-C-NMe2

RuCl 2L3 Tetr Lett,

3,3661

(1982)

Tetr Lett,

3, 3363

(1922)

SECTION 347

AMIDE

- KETONE

47 1

85%

i

C02Me

C02Me T e t r L e t t , -23, 1 2 0 1 ( 1 9 8 2 )

TiC14

+

+

c1

L

N - C 02Me

w

;

j

e

78%

Y-Co2Me Tetr Lett, 21, 2 0 3 3 ( 1 9 8 0 )

Me

d

-

CsF/Si ( O R ) 4

+

0

Ph

86% NEt2

Tetr Lett,

23,

5531 (1982)

472

COMPENDIUM OF ORGANIC SYNTtIETIC METHODS VOL 5

SECTION 347

V

Et3N

Me

<’ ‘0’

0

83%

JOC, -4 6 , 4416 ( 1 9 2 1 )

S e c t i o n 3 4 3 Amide - N i t r i l e No a d d i t i o n a l e x a m p l e s .

S e c t i o n 349 Amide

-

Olefin 1) PhSeC1, CF3S03H CH3CN

2 ) 30% H202 JOC,

46,

4727 ( 1 9 8 1 )

&6% Angew Chem I n t Ed,

2, 630

(1982)

AMINE - ESTER

SECTION 351

Also v i a :

473

O l e f i n i c a c i d s ( S e c t i o n 322)

S e c t i o n 350 Amine

-

Amine

- aNH

1) [CpCo(N0)I2, NO 2 ) LiA1H4

NH2

JACS,

S e c t i o n 351 Amine

-

70%

202,

5676 (1930)

Ester

- PY

1 ) K N C O , ROH

Br

Br

2 ) Conc. HC1 looo

Chem Ber,

ArCH,

NH2

NH2

Jl,

~~50%

173 (1981)

1) BuLi 2 ) MeOCEt2Br

*

:t 1

Et

3 ) H30t

*

MeO-C-CH-COOMe 1

NH2

4) N H 3 , H20 S y n t h e s i s , 965 ( 1921) S y n t h e s i s , 861 and 270 (1982)

95%

95%ee

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

474

$eM

Me0

4

OMe

1) Me2C=0

COOMe

w

OH

Me

Angew Chem Int Ed, I

1) CH3-CH-COOE t i - C H a C 1

Me

2 ) H30t

CH2C1

&

SECTION 351

19,212

(1980)

q; -

OBz

PTC

2 ) HC1, Et20

CH2-C-C02Et I Nti2 HC1

93%

6

Tetr Lett,

23, 4259

(1982)

C

I1

t-BuOC-CH2MgC1 -

+ 8uO-CH-NMe2 Ph I

Me3N t

e

0 t-BuOC-CH2-CH-NMe2 Ph I1

I

76%

Bull SOC C h i m France 11, 395 (1982)

electrolysis

w

Me2NCH2CH(COOEt j 2

i-i2C( COOEt ) Tetrahedron, 37 , 2 2 S 7

( 1981 )

53%

SECTION 352 Review:

AMINE

-

475

ETHER

"Methods o f Synthesis and Properties o f 6-Cimethylaminoethyl and Choline Esters o f Amino Acids and Peptides"

Russ Chem Rev, 50, 1151 (1C81) Related methods: Section 315 (Acid-hide); Section 315 (AcidAmine); Section 344 (Amide-Ester) Section 352 Amine - Ether

71%

Synthesis, 376 (1981)

@:-CH*o*c

MeNHCH2CH20H HCOOH

*

phy:) I

Me

Chem Ber, jl, 2635 (1932)

63%

476

COMPENDIUM

OF

S e c t i o n 353 Amine

ORGANIC SYNTHETIC METHODS

VOL 5

SECTION 353

- Halide Ph

H JOC,

Review:

45,

5328 and 5333 ( 1 9 8 0 )

"The S y n t h e s i s o f o - H a l o g e n a t e d Enamines"

13, 241 (1981) Org P r e p P r o c I n t , -

S e c t i o n 354 Amine

- Ketone

";a OTMS I

-

(33

).A

Me2N=CH2

0

u -

-

NMe2

e '-I"'

W

o r B u O C H ~ N M ? ~ ,TMSI

c

Tetr Lett, Tetr Lett,

21,305 23,

0

(1980)

547 (19C2)

H

0

I1

I1

Ph-C-CH2CH3

+

Ph-C-CH-CH3 I

2 ) NaOH, H20

BCS Japan,

79%

CH2 I

55,

1331 (19G2)

60%

S E C T I O N 354

AMINE

-

KETONE

Tetr Lett,

477

21,809

(1980)

0 S y n t h e s i s , 650 ( 1 9 8 0 )

t

0

OLi\

/ ( EtO) 2p

0

I1 0 0 1) PhCCH2Br, Bu4NBr

2) HC1 , benzene

! S Ph-C-CH2NM3

92%

0 S y n t h e s i s , 922 (1962)

-PiMe

0 L i tMe I l l

I

P h2 P-CH-N-P h

2 ) NH4C1

3) a

79%

Tetr Lett,

22, 2799

(19G1)

478

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 354 NMe2 I

1) LDA, THF

2 ) e C H O CH3-CH-CN I NMe2

3)

72%

A

Tetr Lett,

23,

639 (1982)

Review: "Amino Acids as the Amine Component in the lannich Xeacti on" K u s s Chem Rev, 51, 387 (1582)

Section 355 Amine - Nitrile 1) 30% H202, MeOH

2 ) TFAA, CH2C12

3) KCN, H20

Me

6

73% Me

Synth Cornm, lo, 495 (1980)

Section 355 Amine - Olefin

FI

(Me0)2PCHN2

t-BUOK, Et2NH

Tetr Lett,

4;:

2,2041

(1980)

69%

AMINE

SECTION 356

Oo

OLEFIN

479

2 ) NH4C1

+

92%

3 ) KH

Ph2P-CH-N I

II

0 Li

Zeview:

-

0

I

"Enamines:

Tetr Lett,

21, 2 6 7 1

(1980)

Recent Advances i n S y n t h e t i c , S p e c t r o s c o p i c ,

M e c h a n i s t i c , and S t e r e o c : i e m i c a l A s 9 e c t s . " 38, 1575 ( 1 9 8 2 ) Tetrahedron, 38, 3363 ( 1 9 8 2 ) Tetrahedron, -

-

0

BF3*0Et2 t

BuNH2 S y n t h e s i s , 380 ( 1 9 8 1 )

96%

480

COMPENDIUM

OF O R G A N I C S Y N T H E T I C METHODS V O L 5

S E C T I O N 356

6 s -6 @ COOMe

Me

P d C l ( CH3CN)

1 1 0

2

t

"W

COOMe

7 3%

LiC1, THF

J O C , 46, 2 5 6 1 (1981) I

*

n

Hept

CH2NEt2

PhS-CH2-NEt2 Tetr Lett, 21, 3763 (1980)

N o u v e a u J Chern, 4, 7 2 7 (1980)

95%

SECTION 357

m

ESTER

- ESTER

481

Co-salicylidene 02, MeOH

H

H Chem L e t t , 1237 ( 1 9 8 0 )

QJ

CH31,

Q-

87%

A

S e c t i o n 357 E s t e r

18-crown-6

CH3 3172 ( 1 9 8 0 )

'

- Ester COOMe COOMe

66%

Zn, CH3CN

Chem L e t t , 1217 ( 1 9 8 1 )

COOMe

COOMe

S y n t h Comm,

11,35

(1981)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

482

SECTION 357

1) MeSSMe, S02C12 2) NaCH(COOEt)2 3 ) (Me0)2S02 4) NaOEt

A

Ph

+

COOEt 6 2 % COOE t Synthesis, 690 (1980)

Cu2Br2 DMSO

Br2C( COOEt)2

Ph

COOEt Y C O O E t

B u l l Chem SOC Japan,

1) MeOOC-C- C-COOMe

-

2 ) 150'

+

3, 2539

71% (1981)

Q -

COOMe COOMe 31%

Acta Chem Scand B y 435 (1982)

ESTER - HALIDE

SECTION 359

HC-C-CO2Et EtOH

C-OCH3

*+

483 80%

CH(COOEt)2

OMe Tetr Lett, 3,3765 (1922)

Also via: Dicarboxylic acids (Section 312); Hydroxyesters (Section 327)' Diols (Section 323) Section 358 Ester - Ether -~

1 ) PhI(OAc)2

Ph-CH2COOMe

-

2) NaOMe, MeOH

Ph-CHCOOMe OMe

70%

I

Tetr Lett, --22, 2747 (1981) COOH

-i-PrCHO

96%

P PA

Aust J Chem,

=OE

t

-

HF, SF4

33,

685 (1980)

0

OEt

JOC (USSR), 17,1260 (1931)

25%

484

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 359

PhCH2PdC1 (PPh3)2 Bu3SnC1, Ph-C-C1

P h - ! - O T C i l %

I1

CH3

0 JOC,

47, 1215

-

1) B B r 3 , CH2C12 2 ) FleOH

Br

(1982)

M

COOMe

65%

S y n t h e s i s , 963 ( 1 9 8 2 )

Me3Si I > 90%

EtOH

S y n t h Comm, _II, 763 ( 1 9 8 1 )

c1 LiOAc, L i C l 89%

Pd(OAc)2, HOAc

I

b e n z o q u i none

OAc Tetr Lett,

23, 1617

(1962)

SECTION 359

ESTER

0""

- HALIDE

C1 3CC02Me

485

-0"

c1 i

C - C 0 0 Me

3 1%

Z n , Et2A1C1 , THF

53,

B u l l Chem SOC Japan,

WcooH

H

TlOAc, I 2

0-

CH2C1

A u s t J Chern,

1698 ( 1 9 8 0 )

90%

- *

-

= H 1

2,2793

(1979)

60-90%

JCS Chem Comm, 465 ( 1 9 8 1 )

0 I1

CF2=CH2

C2F5C-OC1

C1F

N aF

0 I1

C2F5C-OCF2CH2C1

JOC, 45, 1214 ( 1 9 8 0 )

Also via:

H a l o a c i d s ( S e c t i o n 3 1 9 ) ; H a l o h y d r i n s ( S e c t i o n 329)

80%

486

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 360

Section 360 Ester - Ketone

FC: C-OMe

BuMgBr +

00 EtO-C-C-OEt

Ph-I=O

RuCl 2L3

THF

2) H30t

60%

C-C -0Me

1

Tetr Lett, 23, 3661 (1982) 00 I,

I1

Bu-C-C-OEt

75%

I1

I1

1 1 , 943 (1981) Synth Comm, -

-

Ph-MgBr

+

00 Ph-C-C-OEt I1

I1

72%

JOC, 46, 211 (1981) Y3 PhCH2CHC02Et

1 ) LiOEt

0 PhCH2C-C02Et 11

2) HC1, H20

w

JOC, 45, 4952 (1980)

( Et0)3CCN

1) BuLi 2) H30t

00 Bu-C-C-OEt 11

I,

Tetr Lett, 22, 1509 (1981)

94%

-

ESTER - KETONE

SECTION 361

Na2PdC1

COOMe

0

407

t-BUOOH -

78%

Chem L e t t , 257 ( 1 9 8 0 )

-

1) Ph3P=CHCOOEt

I1

R-C-C1

2 ) A1-Hg

JOC,

Ph-COC1 t

Zn, PdL4 DME

0I,

OOE t 81-93%

R

47,

4955 a n d 4963 ( 1 9 8 2 )

0I,

* Ph-C-CH2C-OEt

80%

BrCH2C02Et Chem L e t t , 1559 ( 1 9 8 2 )

c

C- S E t

C-OEt

0

1) LDA, THF 2 ) H30t

- Qo COOE t

Tetr Lett,

22,

1353 ( 1 9 8 1 )

74%

438

COMPENDIUM

\\/\

OF

ORGANIC SYNTHETIC METHODS VOL 5

SECTION 360

PPh3 OPh T e t r L e t t , 21, 1475 ( 1 9 8 0 ) c

A u s t J Chem,

33,

113 ( 1 9 8 0 )

SnCl

6 3%

CH2C1 Angew Chem I n t Ed, 20, 537 (1981) HC1, CH30H

):)(

Me-CN

U

3) NaOEt

Et3N

-

0 I1

Me-C-CH2COOEt 85%

4 ) H30t S y n t h e s i s , 130 (1981)

SECTION 360

ESTER

-

KETONE

0

489

0

I1

/C-Ph

i1

NaOMe

‘3COOMe t

7 1%

MeOH

JOC, -45, 264 ( 1 9 8 0 )

NNe2

0

x:;

1) 0 (31-!)-0

0 11

Synthesis, 451 (1982)

NR.

0

JOC,

11

Bz-C-CH2-C-OMe

2 ) MeOH, r e f l u x

2

0

45,

1868 ( 1 9 8 0 )

OTMS

JOC, 46, 2717 ( 1 9 8 1 )

83%

490

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 360

OTMS

-(y

1) TiC14, Ti(O--iyPr)4 t

2 ) H20

C02Me 0

79%

3 ) CH2N2

Chem L e t t , 1043 (1980)

S y n t h e s i s , 223 ( 1981)

0

Chem L e t t , 379 (1982)

Also v i a :

Ketoacids ( S e c t i o n 3 2 0 ) ; Hydroxyketones ( S e c t i o n 330)

SECTION 362

ESTER

-

OLEFIN

49 1

Section 361 Ester - N i t r i l e

Ph

7

CHo

* Ph

A1203

t

Coo"elOO~

0 CN C H 2 COOMe

CN Tetr L e t t , 22, 4927 (1982)

1) LDA

0

76%

C02Et

2,

3) H20

AcD

JOC, 45, 2614 (1980)

HgOAc

H2C=CHCN NaBH4

*

Act52c

Angew Chem I n t Ed,

72%

21, 130

(1982)

Section 362 Ester - Olefin This section contains syntheses o f enol e s t e r s and e s t e r s o f unsaturated acids.

492

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

b

SECTION 362

98%

Amberlys t- 15 Indian

"b

J Chem,

_2E,358

r rcHo JACS,

jg,1966

(1980)

0

S-'-C5H11

I

R

*

(1982)

0 11

CH=CH-0-C 1

Cs F

C5H 11

Chem Lett, 529 (1980)

COOH

1) HS(OTFA)2

2)

Ht

JACS, lE, 5459 (1981)

80%

SECTION 362

ESTER

R e l a t e d methods:

-

OLEFIN

49 3

P r o t e c t i o n o f Aldehydes ( S e c t i o n 6 0 A ) ; P r o t e c t i o n o f Ketones ( S e c t i o n 180A) Ph 7 3%

+ similar Ph-CHO

Ph

*~60%

HMPT JCS Chem Comrn, 277 ( 1 9 8 1 )

B-0

PdC12, NaOAc

yEt

Et

C O Y MeOH

*

9 52

COOMe

Chem L e t t , 279 (1981)

6

- *;is

COOMe

MeO-C-OTMS 3

2) E t 3 N , MeOH

S y n t h e s i s , 58 ( 1 9 6 2 )

87%

494

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 362

H

i

C-COOE t t

8 1%

2 ) H30t

B u l l Chem SOC J a p a n ,

52,3619

(1979)

1) 2 LDA

(E isomer

eBr

i s formed i n 58% y i e l d i f ZnC12 i s o m i t t e d . )

Chem L e t t , 595 (1930)

or

Ni ( C O ) 4 C O Y PdL4

OH

CH3CN

JOC, 4 6 , 1723 ( 1981) 3630 ( 1 9 8 2 ) JOC,

47,

C: CH

P B u 3 , CH3CN

JACS, 103, 7520 ( 1 9 8 1 )

0

72%

SECTION 362

ESTER

Q

I

OMe

"0

2 ) H20, HC1

-

OLEFIN

495

-

pu

50%

Chem Lett, 1567 (1980)

m

88%

Et3N

104,6879

{ICH3 [q JACS,

(1982)

1) TMSCN, KCN

CHO

18-crown-6 2) pyridinium dichromate

DMF

Tetr Lett,

1 ) NaH

Et-CH(COOEt)2

SPh 2) Me-CH-C1 3) NaBr, HMPT

*

270%

0

21, 731

(1980)

,COOEt

MeCH=C,

Et

Synthesi s , 131 (1 982 1

73%

496

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

COOMe

COOMe

COOMe

1) I D A

8 1%

2) E t I

MeOOC

Tetr Lett,

0

4

SECTION 362

Et

23, 3683

(1982)

I1

0CCH20CH3

1) LDA, THF

2 ) HMPA, O2 3) camphorsulfonic a c i d

JOC,

$5,4 1 3 5

COOMe

5 17;

(1980)

76'5

JOC,

45,

00 Na CH( COOMe) PdL4 N02

264 ( 1 9 8 0 )

-

+o

CH(COOMe)*

JCS Chem Comm, 8 2 1 ( 1 9 8 2 )

79 :7

SECTION 364 Also v i a :

ETHER

-

49 7

HALIDE

Acetyl2nic esters (Section 306); O l e f i n i c acids (Section 3 2 2 ) ; B - H y d r o x y e s t e r s ( S e c t i o n 327)

S e c t i o n 363 E t h e r

- Ether

See S e c t i o n 60A ( P r o t e c t i o n o f Aldehydes

and S e c t i o n

80A ( P r o -

t e c t i o n o f K e t o n e s ) f o r r e a c t i o n s i n v o l v ng t h e f o r m a t on o f acet a l s and k e t a l s .

No a d d i t i o n a l examples.

S e c t i o n 364 E t h e r

- Halide Br

B u l l Chem S O C Japan,

Tetr Lett,

s, 219

3 , 2005

(1980)

(1980)

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

498

H2C=C,

,CH20Et CH3

NBS

MeOH

SECTION 364

YH3 BrCH2-C-CH20Et

62%

I

OMe

Z Chem, -_ 20, 209 (1980)

t

KF

( F ~ C2 )

~

~

~

~

~

2

F2C=CFCF20S02F JACS, 103, 5598 ( 1 9 8 1 )

S e c t i o n 365 E t h e r , E p o x i d e

- Ketone

JOC, 46, 3326 ( 1 9 8 1 )

OTNS Ph

t-BuOC1 , PdL4 HgO

n L

~

O

Ph

Chem L e t t , 369 ( 1 9 8 2 )

-

p

B

u 64%

~

~

=

S E C T I O N 365

ETHER, E P O X I D E

-

KETONE

499

&OBz

87%

OTMS

TMSOTf

t

Tetr Lett,

1, 2527

(1980)

(92% e r y t h r o ) JACS, 102, 3248 (1980) NaOH/H20/H202 t o 1 uene, benzyl q u i noni urn

0

chloride

0 92% 45% ee

JOC, 45, 2498 (1980)

wcl

500

COMPENDIUFI OF O R G A N I C SYNTHETIC METHODS VOL 5

SECTION 365

NaOCl

Bu4NBr CH2C1

0

0 Gazz Chim I t a l

, jg,267

(1980)

E t h e r , E p o x i d e - N i -trile S e c t i o n 366 -~

~-

1) MCPBA 6 7% 2) !le3SiCN, Zn12 Tetr Lett, 22, 4925 (1981)

0

C1 CH2CN

,

NaOH

P.T.C.

4'

B u l l Chem SOC Japan,

53,

76%

1463 ( 1 9 8 0 )

SECTION 367

ETHER

- OLEFIN

50 1

S e c t i o n 367 E t h e r

- Olefin

R e l a t e d methods:

P r o t e c t i o n o f Ketones ( S e c t i o n 180A).

Hx

cat. CU(OAC)~ 56%

02, MeOH

K2

Tetr Lett,

0 t-BuOK, ( Me0)2PCHN2 " R-OH

R = __ t-Buy a l l y 1

OMe

fly 4105

-6

Tetr Lett, Tetr Lett,

JACS,

OR ~60%

fly 2041 1, 5003

104,5842

(1980)

(1980) (1980)

(1982)

NaBH4 , hv DCNB, MeCN/H20

JOC, 46, 788 ( 1 9 8 1 )

502

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 367 OMe

Organometall i c s , 1,1467 (1982) Tetr Lett, 3,323 (1982)

A

s

OB u

-

KOH, n

A

w

II

0

JOC (USSR),

TMS

t

CH(OMe)2

Ph

0

By395

Tetr Lett,

(1922)

OMe

Me3Si I CH2C1

68%

OB u

Ph

22, 745 (1921)

1) C1 CH=CHCH2TMS A1 C1

2) NaBH4, MeOH 3) NaOH Tetr Lett,

74%

2, 4369 (19EO)

SECTION 368

HALIDE

COOEt

-

HALIDE

503

hv A

tOOC

COOEt

74%

Chem Ber, 114, 3725 (1931) ~

O2 OAc

+

LFe30(OCoR) gL3$

A

O

A

c qd70%

JACS, _1l, 6450 (1982) Section 368 Halide - Halide Halocyclopropanations are found in Section 74 (Alkyls from Olefins).

JOC, 46, 3917 (1981)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

504

1 ) LiCH(TePhI2

R-X

R = '1

2) Br2, NaBr

-

alkyl

SECTION 368

R-CHBr2

76-85%

Chem Lett, 1081 (1982) F

Tetr Lett,

1, 4543

(1980)

Amberlys t A-26):1(CI

752

CH2C1 JCS Chem Comm, 1278 (1980)

Me00C MeOOC

electrolysis NaBr, H 2 S 0 4 , H20/MeCN

MeOOC MeOOC

JOC, 46, 3312 (1981)

92%

" Br

HALIDE - H A L I D E

SECTION 368

8u-CH=CH2

CH2C1 I

505

Bu-CH-CH2-CH2

A 1 BN

I

I

81 %

I

c1

8 u l l Chen SOC Japan, 53, 770 (1980)

t-BUOC1

-

s i l i c a gel

c1

42%

Chem L e t t , 141 (1982)

CH20Ac

Me3Si Br

I

By-

( C H 2 ) 3 CH I

872

Br

oCH20A~ S y n t h e s i s , 383 ( 1981

Br CuBr2, Me3CON0 CH3CN

-

99%

Br@r

CH3

CH3 JOC,

35,2570

(1980)

506

COMPENDIUM

OF O R G A N I C S Y N T H E T I C METHODS VOL 5

JOC,

S e c t i o n 369 H a l i d e

-

47,

S E C T I O N 368

4770 ( 1 9 8 2 )

- Ketone

J A C S , 102, 4845 (1980) ~

so2c1 9 5%

c1

SO2, MeOH JOC,

b -6 JOC,

$6, 4486

(1981)

CUCl DMF

45,

2022 (1980)

58%

HALIDE - KETONE

SECTION 369

J05 0

HO

cl+cl c1

n,

507

c1

c1 90%

E tOH

HO Synthesis, 1018 (1982)

a,

Amber1 ys t A- 26 (perbromide or IC1) 45% ( X 90% ( X

= =

C1)

Br)

JCS Chem Comm, 1278 (1930) Synthesis, 143 (1980)

or NC-CBr2-C-NH2 -

1

I1

0

Indian J Chem, 17B, 305 (1979) Synthesis, 487 (1980) n

Synthesis, 312 (1981)

508

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 369

Pb(OAc)4

87%

NaI, MeOH Synthesis, 1021 (1982)

hv, 02

54%

FeCl 3, pyridine JOC,

46,

509 (1981)

Tetr Lett,

21, 4521

(1980)

I) Me3SiI

2) Cr03, H2S04

Tetr Lett, 22, 1429 (1981)

91%

SECTION 369

9

HALIDE - KETONE

509

83%

‘gHll

JOC,

95,

2731 (1980)

HOCl w

Tetr L e t t ,

75%

22,

5019 (1981)

Br2, HBr 68% electrolysis

Q

Synth Comm,

lo, 821

(1980)

n

$ 0 PhNMe3Br3

HOCH2CH20H/THF

S y n t h e s i s , 309 (1982)

89 %

510

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 369

PhSeBr CH2C1 ,$pyridine

100%

or 1) Br2 2 ) E t 3 N T e t r L e t t , 2, 3301 (1981) JOC, 47, 5088 (1982)

Tetr L e t t ,

21, 2639

(1980)

1) Me3SiC1 , E t 3 N 2 ) CH212, E t 2 Z n

>80%

3 ) FeC13, DMF

Org Syn,

2, 113

(1980)

C1 CH2CN OH

85%

BC13, A1C13 11

C1 CH2CH2C1 JOC,

0

46,

189 (1981)

SECTION 3 7 1

HALIDE

-

OLEFIN

511

C1 3 C B r , Pd( OAc)

+ OH

80%

lc+

0

Chem L e t t , 1605 ( 1 9 8 1 ) Review:

"F1 u o r i n e - C o n t a i n i ng 6 - D i k e t o n e s " Russ Chem Rev, 50, 180 ( 1 9 8 1 )

S e c t i o n 370 H a l i d e

- Nitrile

No a d d i t i o n a l examples. S e c t on 371 H a l i d e

- O l e f-in

C

H e l v Chim A c t a ,

63,

1236 ( 1 9 8 0 )

512

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 5 c1

n-C8H 17E1gC1

w

c1 cr

N i L4

SECTION 3 7 1

m

n-C H 8 17

c1

65%

T e t r L e t t , _22, 3 1 5 (1981) H-C-C-CH2TMS t

TiC14

cr

BuCH=CH-C=CH2

72%

I

c1

Bu-CHO

22, 453 ( 1 9 8 1 1 T e t r L e t t , -_-

Z Chem, 22, 1 2 6 ( 1 9 8 2 )

NaOMe

Br

MeOH

93% Br

NaOMe 74% MeOH

S y n t h e s i s , 999 (1981)

SECTION 3 7 1

Hx-C-CH

HALIDE

@H B r 2 o Bu4N CH2C 1

-

OLEFIN

Hx, Br

513

,C=CH2

80%

S y n t h e s i s , 805 ( 1 9 8 0 )

aCH

1) Br2CHLi

2)

Zn, HOAc

68%

*

22,

Tetr Lett,

3745 ( 1 9 8 1 )

77% Tetr Lett,

1, 4021

(1980)

1 ) catecholborane

70% S y n t h Comm, 1 1 , 247 ( 1 9 8 1 )

1 ) LiPh2Cu Me i e * = CpFe(C0) (PPh3)

2) I2

Me,

*

C

,Ph

y C \ Me I,

-

JACS, 102, 5923 ( 1 9 8 0 )

21

70%

514

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

SECTION 371

Can J Chem, 6 0 , 210 (1982) c

so2c1

Ph

Ph-C-C-Me

85%

c1

He

B u l l Chem SOC J a p a n , Amberlyst A-26 (perbromide form)

Bu-CZCH

Bu

3, 2843

‘C=CHBr

(1931)

94%

Br’

S y n t h e s i s , 143 (1980)

Bu, H

,c=c.

Bu,

,SiMe3

c1 /

=c

c1

’ B\

1 ) Br2 2 ) NaOMe, MeOH

I

1 ) Me3N+0 2 ) Br2 3 ) NaOMe

*

* Bu, H

Bu, H

,c=c

/

,C=C,

c1 Br

,Br

‘c

1

S y n t h e s i s , 1 2 7 (1982)

73%

80%

SECTION 371

L ' %cl c1

HALIDE

c1

-

OLEFIN

"kFil

BOO

+

515

-

c1

51%

c1

Angew Chem I n t Ed, -19, 138 (1980)

( C 1 3c)2c=o

Jw OH

Ph$J,

290%

Q-

o" "o

JOC, 46, 824 (1981)

w

c1

1) L D A

81%

*

2) B u B r

c1 JOC,

46,

1504 (1981)

Me

JOC,

95,

2566 (1980)

516

COMPENDIUM

OF

S e c t i o n 372 K e t o n e

5H 11

Ph-C-C-C

ORGANIC SYNTHETIC METHODS VOL 5

- Ketone 0

PhIO n,.ri

Ph

I

nUL'2L3 2 PhI(OCOCF3)2 C H C l 3/H20

*

54,2531

00 I1

72%

0

H e l v Chim A c t a , Ph-C-C-Ph

SECTION 372

(1981)

I1

82%

Ph-C-C-Ph

D o k l a d y Chem, __ 245, 140 (1979)

P h - C - N+O

n t

s@

Ar

0

2 Ph-i-Cl

00 II

I1

2) CF3C02H

+

Ph-C-C-Ar

~60%

CH20, H20 Tetr Lett, 21, 1747 (1980)

Sm12

00 II

II

Ph-C-C-Ph Tetr Lett, 22, 3959 (1981)

78%

SECTION 372

KETONE - KETONE

51 7

co

2

HMPT/THF

96%

JOC, 47, 4347 (1982) I

0

0

Tetr Lett, 21, 3479 (1980)

1 ) B r 2 , Et20 2) NaOH, THF/H20

65%

Chem Lett, 779 (1980)

T1 ( O A C ) ~

AcOH 0

w

aof!’.

Chem Lett, 305 (1980)

71%

518

COMPENDIUM n

Hx

OF

ORGANIC SYNTHETIC METHODS VOL 5 0

Na2PdC1

w

t-BuOOH

Hx

SECTION 372 0

AA

59%

Chem Lett, 257 (1980)

PdL4

62%

Ph2PCH2CH2PPh2 JACS, -102, 2095 (1980)

py

CH2-(acac)Nitf

t

Ph

wN02

73%

N02

Synthesis, 467 (1982) 0 I1

1 ) CH3C-CN, TiC14 ..go%

2) H20,HO'

Tetr Lett, 22, 1171 (1981)

KETONE - K E T O N E

SECTION 372

6

519

0 CH3C-C1 I,

65%

SbC13

JOC, 47, 5099 ( 1 9 8 2 )

0

0

v

55%

JOC, _46, _ 3771 ( 1 9 8 1 )

OBEt2

3

‘gH1 1

1 ) CH3CN 2 ) H30t

‘gHll

Et

CH3

83%

Et

Synth Comm, __ 1 2 , 189 ( 1 9 8 2 )

P h - N-TMS

KF, crown e t h e r , C H 2 C 1 2

Tetr L e t t , -23, 3073 ( 1 9 8 2 )

93%

520

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

ro

F

SECTION 372

CF

CF2CF3 80%

BCS Japan, 55, 3345 (1982)

1) LiN(TMS)*

Ph

CH3

00 2) Ph-C-P(OEt)2 I1

*

Ph

I1

uph

Chem Lett, 1087 (1981)

Ph-CHO -t

2) Rh(OAc)2

Li

1

*

Pr

DME

JCS Perkin I , 2566 (1981)

0

KHS04

OH

CH20Me

b

Chem Lett, 551 (1981)

86%

SECTION 372

KETONE

- KETONE

521

OH Tetr Lett, 22, 3699 ( 1 9 8 1 )

PdC12, CuC1,

c6H1&A

H20/di oxane

O2 c6H+

0

61%

Chem L e t t , 8 5 9 ( 1 9 8 2 )

45-73%

28, 262 ( 1 9 8 0 ) Chem Pharm B u l l , -

JOC, 45, 5408 ( 1 9 8 0 )

522

COMPENDIUM

OF O R G A N I C S Y N T H E T I C METHODS V O L 5

S E C T I O N 372

Synthesis, 413 ( 1 9 8 0 )

H2C=C,

4

CH3

SnC14

Org Syn,

m

60,

6

1

117 ( 1 9 8 1 )

-

7

0

%

S E C T I O N 372

KETONE

-

KETONE

B G 1 ) CH3CH0, Et2NH2C1

0 ,I

CH3-C-CH3

2 ) KF, 18-crown-6

523

*

0

I1 ?3 CH3-C-CH2-CH-C-CH3 ,I

0

3 ) CH3CH2N02 4) KMn04-silica gel JCS Chem Comm, 635 ( 1 9 8 2 )

n

t

Qo

JCS Chem Comm, 122 (1981 )

hH

N

II

1)

Me’

C

t-Bu OMe

\(CH2):

+uLi e

2) H30t

(j& 89% 75% ee

Tetr Lett, 23, 3711 ( 1 9 8 2 )

80%

524

+

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

Bu3B

2) MVK, TiC14

-I

3 ) H202

C 5H 1 1 -C=CH

SECTION 372

* Bu

‘gH1 1

58%

Chem Lett, 221 (1980)

OMe

92% Synth Comm, 10, 9 (1980)

Chem Lett, 725 (1980)

Section 373 Ketone

b

-

Nitrile

0

t-BuNC TiC14

84%

CN JACS, __ 104, 6449 (1982)

SECTION 374

KETONE - OLEFIN

525

Comptes Rendus, 291 , 179 (1980) c

0 CH2=CHCN

NaCN, DMF

68%

Org Syn, 59, 53 (1980)

S e c t i o n 374 Ketone

-

Olefin

For t h e o x i d a t i o n of a l l y l i c a l c o h o l s t o o l e f i n i c k e t o n e s , s e e S e c t i o n 168 (Ketones from Alcohols and P h e n o l s ) . For t h e o x i d a t i o n o f a l l y l i c methylene groups ( C = C - C H 2 s e e S e c t i o n 170 (Ketones from A1 kyls and Methylenes).

-f

C=C-CO),

For t h e a l k y l a t i o n of o l e f i n i c k e t o n e s , s e e a l s o S e c t i o n 177 (Ketones from Ketones), and S e c t i o n 74 ( A l k y l s from O l e f i n s ) f o r conjugate alkylations.

526

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

SECTION 374

CO, LiCl

2

[Rh(C0)2C112, THF

HgCl

c=o JOC, 45, 3843 (1980)

JACS, __ 102, 3848 (1980)

O=C-CH3 I

JOC, 47, 5393 (1982)

0

Tetr Lett, 22, 5127 (1981)

SECTION 374

)1(

KETONE - OLEFIN

I

Ph-CH=CH-CHCN

1 ) LDA 2) EtBr 3) H20

+

527

0 I1

Ph-CH=CH-C-Et

78%

4) CU(OAC)~,EtOH Chem Lett, 1263 (1982)

Tetr Lett, 23, 2105 (1982) 0

0

DBN or DBU

JOC, 47, 4358 (1982)

Tetr Lett, 22, 3043 (1981)

95%

528

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

SECTION 374

Synth Comm, 10, 667 (1980)

0

a}

PhSeSePh Ph1O2

a}

+

$80%

0

JCS Chem Comm, 1044 (1981) CH2-CH2 I

I

Pd(OAcI2, PPh2 PPh2 CH3CN JACS, 104, 5844 (1982)

0

a}

SECTION 3 7 4

H N - 0C" .- N H N

- OLEFIN

KETONE

529

1 ) Pb(OAc)4 HOAc

*

2 ) O' H

0

Tetr Lett, 21, 651 ( 1 9 8 0 )

0 3

0

NaOH t

72%

EtOH

Ph-CHO

Ph S y n t h e s i s , 647 ( 1 9 8 0 )

PhCH2CH2CH0

LiI

t

ether

0

PhCH2CH2

75%

I,

CH3CCH3

n

JCS Chem Comm, 486 ( 1 9 8 0 )

n

2

CH3

2'3

S y n t h e s i s , 60 ( 1 9 8 2 )

63%

530

C O M P E N D I U M OF

ORGANIC S Y N T H E T I C METHODS V O L 5

(HCHO)

SECTION 374

*

8

.80-90%

CF3COOo MeNH2Ph

Org Syn, 60, 88 ( 1 9 8 1 )

Ph

Ph2C0

0

t

BrCH2C-CH

Synth Comm, --10, 637 ( 1 9 8 0 )

@

0

P

6-Cl

(y

A TMS

56%

SnC14

JOC, 45, 1046 (1980)

, COC 1

1 ) Me2C=C H‘ 2 ) SnC14 TMS

3 ) RhC13

~

(@

JOC, 45, 3017 (1980)

70%

SECTION 374

KETONE

- OLEFIN

EtC-CEt

Ni ( C 0 l 4

WEt

531

89%

Et JOC, 45, 5426 ( 1 9 8 0 )

Me2N-CH-CN

1 ) P205

LDA ZnC12

w

w

2 ) K2C03

94%

0

Tetr Lett, 21, 1205 ( 1 9 8 0 )

‘gH1 1

4

Hg (OAc1

‘gH1 1

Tetrahedron, 36, 189 ( 1 9 8 0 )

70%

532

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

x

SECTION 374

H-CiC-CH3

cocl

53%

A1C13 Tetr Lett, 23, 4923 (1982)

0

0

, H2C=C=C, t

TMS

Me

Ti C1

85%

CH2C1

JACS, 103, 1604 (1981) CHO Ph-bH-CH3 t

H2S04

74%

benzene Ph

CH,J

JOC, 45, 5399 (1980)

SECTION 374

-

KETONE

OLEFIN

533

rco Ph3P=C=C=NPh t

72%

Angew Chem I n t Ed, 19, 822 ( 1 9 8 0 )

@'

-

MeS03H '2'5

0 0

65%

Tetr Lett, 22, 2459 (1981 )

3 ) CH3CN,

AgOAc S y n t h e s i s , 289 and 291 ( 1 9 8 1 )

MeAl( OCOCF3)

OfMS

65%

0 B u l l Chem SOC Japan, 53, 2050 ( 1 9 8 0 )

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

534

SECTION 374

OCH0 1) 0 - H

2) MVK

3) NaOAc, AcOH/H20 @oIera1 4) NaOH 5 ) DDQ Org Syn, 61, 129 (1983)

H C I

111

NaH, 125'

80% Tetr Lett, 21, 2123 (1980)

- &

1) KH, THF 2) NH4C1

22, 2471 (1981 Tetr Lett, -

/CH(S02Ph)2

90%

1) 5% @-Pd 2) Me2S0,

0

Et3N

60%

JACS, 104, 6112 (1982)

S E C T I O N 374

KETONE

- OLEFIN

535

0 i-Bu2A10Ph b

Hexane/THF pyridine, A (mixture o f E and Z p l u s some

B ,r-i somer )

6

B u l l Chem SOC Japan, 53, 1417 ( 1 9 8 0 ) 1 ) BuMgBr, CuCl 2 ) MeSOCl

76%

3 ) CaC03, t o l u e n e

- -L Chem L e t t , 1159 ( 1 9 8 1 )

n

-

1) 2 ) 5% HC1

B r , LDA

90%

- THF

Chem L e t t , 165 ( 1 9 8 2 )

0

S y n t h e s i s , 473 ( 1 9 8 1 )

536

-

SECTION 374

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

1 ) LDA

PhSe

SePh

2)

L,

w

Br

3 ) H202

0 JOC, __ 47, 1 6 1 8 ( 1 9 8 2 )

Zn ( O A c )

78%

Gazz Chim I t a l , 112, 1 ( 1 9 8 2 )

1 ) Nay NH3

2 ) C7H15Br

C 7 H 15

3 ) H30t

0 i . g Syn, -61, 59 (1983)

%50%

SECTION 374

KETONE

OTMS

- OLEFIN

537

Hg ( OAc 1

97%

PdC12-CuC12

Tetr Lett, 21, 4283 ( 1 9 8 0 )

1 ) PhSeCH2CH0

832

2) MeS02C1 Et3N

JCS Chem Comm, 434 ( 1 9 8 1 )

CH3CH2CH2CN t

w

Br

1 ) Zn(Ag) 2 ) NH4C1, H20

*

A

80%

Tetr Lett, 22, 649 ( 1 9 8 1 1

Ph

0 60%

Chem L e t t , 1483 ( 1 9 7 9 )

COMPENDIUM

538

OF

ORGANIC SYNTHETIC FIETHODS VOL 5

SECTION 374

OLi

Pd(dbaI2

t

55%

dppe, THF

JCS Chern Comm, 1159 (1981)

OTMS 71%

Zn12 Synth Comm, 1 1 , 217 (1981)

1 ) Cp2ZrC1H

+CC-CH 2

i

~

o Ni(I1 ,

3) H30+ JACS , __ 102, 1334 (1980)

78%

SECTION 374

-

KETONE

OLEFIN

539

- o(0,

PdL4 DMF

96%

JACS, 102, 6381 ( 1 9 8 0 )

PPh3

100%

Tetr Lett, 21, 3199 ( 1 9 8 0 )

mo2 +

1 ) A1C13, CH2C12

2 ) TiC13, Ht

62%

Me C‘ 0’

A ‘

Tetr Lett, 2 2 , 1115 ( 1 9 8 1 )

CH2CH2CH3

Ph,P=CH,

Me

FH2 C-CH2CH2CH3

\ /

u

J Chem R e s e a r c h ( S ) , 248 ( 1 9 8 2 )

95%

540

COMPENDIUM

OF O R G A N I C SYNTHETIC METHODS VOL 5

S e c t i o n 375 N i t r i l e

-

S E C T I O N 375

Nitrile

C'

N

92%

CN

Me Br

A c t a Chem Scand B, 34, 289 ( 1 9 8 0 )

S e c t i o n 376 N i t r i l e

- Olefin

79%

JACS, 104, 1560 ( 1 9 8 2 )

Br

KC N

CN

+

N i Br2L2-Zn-PPh3

Chem L e t t , 1565 ( 1 9 8 2 )

JACS, 103, 5568 (1981

85%

S E C T I O N 376

NITRILE

- OLEFIN

541

1 ) (TMS)2C=C=N-TMS BF3 * E t 2 0

2.60%

2 ) NaOH, MeOH JCS Chem Comm, 56 ( 1 9 8 2 )

&

Ph2S=NH

85%

CHo

S y n t h e s i s , 1005 ( 1 9 8 0 )

1 ) TMSCN, Zn12

82%

2 ) P0Cl3, pyridine

Chem L e t t , 1427 ( 1 9 7 9 )

PhCH2CN

Ph

52% NaOH/H2G

*

-I

Ph-CHO

toluene/PEG

b C H P h

NC

S y n t h e s i s , 913 ( 1 9 8 1 )

71%

542

COMPENDIUM OF ORGANIC SYNTKETIC METHODS VOL 5

SECTION 376

-

0

1) Me2N=CC12

CONH2

Me02C

2 ) pyridine

Me02C

CN 90%

Synth Comm, 10, 479 (1980)

JCS Perkin I, 2516 (1980)

R

CN PdL4

t

NaH

CN

OMe Tetr Lett, __ 22, 2573 (19811

SECTION 377

OLEFIN

S e c t i o n 377 O l e f i n

- OLEFIN

543

- Olefin

75%

JOC, 47, 3364 ( 1 9 8 2 )

T e t r L e t t , __ 21, 5019 ( 1 9 8 0 ) Me

Ph-ZnC1

I

Me-C-C-C-H

PdL4

I

Br

Me,

*

Me’

C=C=CHPh

80-95%

T e t r L e t t , --22, 1451 ( 1 9 8 1 ) 1 ) CH3Li

Ph

2)

I

Bu-C-C-C-OH

CUI

Bu

*

3 ) CH3Li

I

CH3

Me

‘c+c

’

M ,e

82%

‘Ph

4 ) P.T.C. JOC, 45, 4536 ( 1 9 8 0 )

‘gH1 3

L

BuBr

7 Li

‘gH1 3

- L

7 Bu

12, 739 ( 1 9 8 2 ) S y n t h Comm, -

842

544

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 5

C 5H 1 1 -C:C-CH2Br t

SECTION 377

CrC12

78%

Tetrahedron, 37, 1359 (1981)

0

HCsC

t

cat. CuI

BuMgBr H 0 Me 2C=C=C ‘Li .t

Ph-I

+

Bu-CH=C=CHCH2COOH

971

Tetr Lett, 22, 2375 (1981)

PdCl 2L2 A1 H(i- 6 ~ ) ~

+ Me C=C=CHPh

2

Synthesis, 738 (1982)

Bu3SnH, AIBN

22, 2675 (1981) Tetr Lett, -

90%

SECTION 377

OLEFIN

0 "c;

HO

JeJ

545

T i C l 3 / L i A 1 H,

75%

THF

104, 5807 ( 1 9 8 2 ) JACS, __

50% NaOH

t

c1

- OLEFIN

w

CHo

9

HC=CH-CH=CH

1

78%

c1

Tetr Lett, 2 1 , 1375 (1980)

2 Bu-CzCH

2 ) NaOMe 3 ) CuBr-SMe,

w L

Bu

9? 2

JOC, 45, 549 a n d 550 ( 1 9 8 0 )

Bu

546

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 5

m

Bu

B(Sia)2

Hex

PdL4

t

Bu

NaOEt

r-7 Hex

Br

Tetr Lett, 22, 127 ( 1 9 8 1 )

L

1

2 ) Me2CHCH0

3 ) KH

I

S E C T I O N 377

1 ) Bu3SnC1 -BF3 2 ) CgHl9CHO

v -

C9H19

* \-

3 ) KH

JCS Chem Comm, 1326 ( 1 9 8 2 )

2% N i ( a c a c ) 2

PhS02

THF 80% Tetr Lett, 23, 2457 ( 1 9 8 2 )

OLEFIN -

SECTION 377

$1)

m

M

OLEFIN

547

n

S

3 ) NaH

!!-c7H1 5

%60%

t

2 ) triethanolamine

n-C7H11 5-CH0

!-c7H1 5

w /

Tetr Lett, 22, 2751 ( 1 9 8 1 ) Me

I PdL4

- MH Et

70%

Tetr Lett, 23, 1591 ( 1 9 8 2 )

Zn12 t

I

PdL4

Et

‘gH1 1

+

Et

Tetr Lett, 22, 959 ( 1 9 8 1 )

86%

COMPENDIUM OF O R G A N I C SYNTHETIC METHODS V O L 5

548

OAc

1 ) fiCO

2 C H ? CC13

2 ) PdL4, E t 3 N

S E C T I O N 377

-0

87%

JACS, 102, 2841 ( 1 9 8 0 )

-

Review:

Ph

-

" P a l 1 a d i u m - c a t a l y z e d Syntheses o f C o n j u g a t e d D i e n e s "

P u r e and Appl Chem, 53, 2323 ( 1 9 8 1 )

1 ) BuLi 2 ) Bu3SnCH21

S

H C=C=C /CgH1 1 2

Ph

Tetr Lett,

-SiMe3

BF3 - HOAC CH2C12

Synth

73%

3,2205

(1982)

dc5H

Comm, 12, 409 ( 1 9 8 2 )

80%

SECTION 377

OLEFIN

- OLEFIN

549

23, 3277 (1982) Tetr Lett, -

+

3 MeCu

BU

72%

JOC, 45, 1640 (1980)

DMF

63%

Organometallics, -1 , 259 (1982)

Hx

-

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O L 5

550

1 ) MeLi

-

Bull

OAc

Ph

SnBu,

\

89%

Chem SOC Japan, 53, 1471 ( 1 9 8 0 )

PdL4

+

&

Br

2,

Hx

*

SECTION 377

-

Ph

THF 3

69%

Tetr Lett, 21, 2591, 2595, and 2599 ( 1 9 8 0 )

Br

CuI

-

CR2 Synth

Bu

Comm, 12, 813 ( 1 9 8 2 )

wc 1 JACS, 103, 1969 ( 1 9 8 1 )

/

43%

SECTION 377

2

2

8 6

GX H

X =

OLEFIN - OLEFIN

551

JCC, 47, 1541 (1982)

NbCl

75%

NaAl H4 Chem Lett, 157 (1982)

vacuum p y r o l y s i s

X

-CH20H, -COOH, -COOMe

X

30-87%

JCS Chem Comm, 325 (1982)

0

JOC, 45, 2721 (1981)

552

COMPENDIUM

Review:

OF O R G A N I C SYNTHETIC METHODS VOL 5

"The S y n t h e s i s o f L e u k o t r i e n e s :

S E C T I O N 377

A New C l a s s o f B i o l o -

g i c a l l y A c t i v e Compounds I n c l u d i n g SRS-A" Chen SOC Rev, 11, 321 ( 1 9 8 2 ) I