General and Synthetic Methods Volume 10

652 Pages·8.098 MB·English

General and Synthetic Methods
Volume 10

A Specialist Periodical Report
General and Synthetic Methods
Volume I 0
A Review of the Literature Published in 1985
Senior Reporter
G. Pattenden, Department of Chemistry,
University of Nottingham
Re porters
K. Carr, University of Nottingham
K. Cooper, Pfizer Central Research, Sandwich, Kent
D. J. Coveney, University of Nottingham
S. G. Davies, University of Oxford
T. Gallagher, University of Bath
L. M. Harwood, University of Oxford
D. W. Knight, University of Nottingham
T. V. Lee, University of Bristol
S. G. Lister, Wellcome Research Laboratories, Beckenham, Kent
K. E. B. Parkes, Roche Products Limited, Welwyn Garden City,
Herts.
N. Simpkins, Queen Mary College, University of London
P. J. Whittle, Pfizer Central Research, Sandwich, Kent
.
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"-a.
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SOCIETY OF
EM I STRY
ISBN 0-85 186-9 14-9
ISSN 0141-2140
Copyright 0 1988
The Royal Society of Chemistry
All Rights Reserved
No part of this book may be reproduced or transmitted
in any form or by any means-graphic, electronic,
including photocopying, recording, taping or
information storage and retrieval systems-without
written permission from the Royal Sociery of Chemistry
Published by The Royal Society of Chemistry,
Burlington House, London, W 1V OBN
Printed in England by Staples Printers Rochester Limited,
Love Lane, Rochester, Kent.
Introduction
This tenth Report on General and Synthetic Methods, and the second
volume to be produced from camera-ready copy of manuscripts,
covers the literature from January to December, 1985.
The general aim of the Reports remains as set out in earlier
volumes. Whilst our contributors strive to provide a critical and
comprehensive summary and assessment of reactions and methods in
synthetic organic chemistry which appear to be useful to the
practitioner, this task has become increasingly onerous with time,
as a consequence of the explosive and rapid development in the
subject over the past decade or so. Nevertheless, these features,
together with the theme of 'selectivity' i.e. chemo-, regio-,
diastereo- and enantio-selectivity, in organic synthesis remain as
our prime focus. We welcome any comments and suggestions for
improving the coverage and presentation of future Reports in this
series.
G. Pattenden
V

Contents
Chapter 1 Saturated and Unsaturated Hydrocarbons 1
By N. Simpkins
1 Saturated Hydrocarbons 1
2 Olefins 1
3 Conjugated 1,3-Dienes 11
4 Non-conjugated Dienes 13
5 Allenes 17
6 Alkynes 21
7 Enynes and Diynes 24
8 Polyenes 26
Chapter 2 Aldehydes and Ketones 32
By K.E.B. Parkes
1 Synthesis of Aldehydes and Ketones 32
Oxidative Methods 32
Reductive Methods 35
Methods Involving Umpolung 36
Other Methods 38
Cyclic Ketones 43
2 Synthesis of Functionalized Aldehydes and
Ketones 47
Unsaturated Aldehydes and Ketones 47
a-Substituted Aldehydes and Ketones 49
Dicarbonyl Compounds 55
3 Protection and Deprotection of Aldehydes and
Ketones 57
4 Reactions of Aldehydes and Ketones 59
Reactions of Enolates 59
Aldol Reactions 64
Conjugate Addition Reactions 66
Chapter 3 Carboxylic Acids and Derivatives 75
By D.W. Knight
1 Carboxylic Acids 75
General Synthesis 75
Diacids 77
Hydroxy-acids 78
Keto-acids 83
Unsaturated Acids 83
Anhydrides 86
Carboxylic Acid Protection 86
Decarboxylation 87
2 Carboxylic Acid Esters 88
Ester ification 88
General Synthesis 90
vii
viii Contents
Diesters 93
Hydroxy-esters 96
Keto-esters 101
Unsaturated Esters 109
Aromatic Esters 117
Acetylenic Esters 120
Allenic Esters and Dienoates 120
Thioesters 122
3 Lactones 124
0-Lactones 124
Butyrolactones 124
a-Methylenebutyrolactones 135
Butenolides 136
Tetronic Acids 140
Phthalides 142
Valerol actones 142
Macrolides 146
4 Carboxylic Acid Amides 150
General Synthesis 150
Hydroxy-amides 151
Keto-amides 153
Unsaturated Amides 153
Thio- and Seleno-amides 156
5 Amino-acids 156
a-Amino-acids 156
B-Amino-acids 165
y -Amino-acids 167
Unsaturated a-Amino-acids 167
Carboxylic Acid Protection 169
Amino Group Protection 169
Thiol Group Protection 172
Chapter 4 Alcohols, Halogeno-compounds, and Ethers 187
By L .M. Ha rwood
1 Alcohols 187
Preparation by Addition to Alkenes 187
Preparation by Reduction of Carbonyl Compounds 187
Chemoselective Carbonyl Reductions 188
Stereoselective Carbonyl Reductions 188
Asymmetric Carbonyl Reductions 190
Enzymic Asymmetric Carbonyl Reductions 192
Preparation by Nucleophilic Addition 192
General Methods of Preparation 203
Protection and Deprotection 205
Reactions of Alcohols 207
Oxi da t ion 207
Hydrogenation and Deoxygenation 208
Miscellaneous Reactions 2 08
2 Halogeno-compounds 212
Preparation from Alcohols 212
Interhalide Conversions 214
Miscellaneous Preparations 214
React ions 216
Dehalogenation 216
Acylation and Coupling Reactions 216
Miscellaneous Reactions 218
3 Ethers 218
Preparation 218
Reactions 220
4 Thiols and Thioethers 222