Lewis Acid Reagents - A Practical Approach

273 Pages·2003·3.683 MB·English

by  H. Yamamoto

Lewis Acid
Reagents
A Practical Approach
Edited by
HISASHI YAMAMOTO
Graduate School of Engineering
Nagoya University
OXPORD
UNIVERSITY PRESS
The Practical Approach in Chemistry Series
SERIES EDITORS
L. M. Harwood C. J. Moody
Department of Chemistry Department of Chemistry
University of Reading University of Exeter
The Practical Approach in Chemistry Series
Organocopper reagents
Edited by Richard J. K. Taylor
Macrocycle synthesis
Edited by David Parker
High-pressure techniques in chemistry and physics
Edited by Wilfried B. Holzapfel and Neil S. Isaacs
Preparation of alkenes
Edited by Jonathan M. J. Williams
Transition metals in organic synthesis
Edited by Susan E. Gibson (nee Thomas)
Matrix-isolation techniques
Ian R. Dunkin
Lewis acid reagents
Edited by Hisashi Yamamoto
Organozinc reagents
Edited by Paul Knochel and Philip Jones
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in order to ensure its continuing availability
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Preface
Lewis acids are becoming a powerful tool in many different modern reactions,
such as the Diels-Alder reactions, Ene reactions, Sakurai reactions, and Aldol
synthesis. In fact, the importance and practicality of Lewis acid reagents as
valuable means of obtaining a variety of organic molecules is now fully
acknowledged by chemists in the synthetic organic society. This prominence is
due to the explosive development of newer and even more efficient methods
during the last decade, and the numbered publications on these reagents is
actually increasing exponentially each year. Research on asymmetric synthesis
has become more important and popular in the total synthesis of natural
products, pharmaceuticals, and agricultural agents, and Lewis acid chemistry
plays a major role in this arena.
Comprehensive coverage of the literature on each area of Lewis acid is not
necessarily provided here. Rather, the aim of the book is to furnish a detailed
and accessible laboratory guide useful for researchers who are not familiar
with the benefits of Lewis acids. It includes information on reagent purifica
tion, reaction equipment and conditions, work-up procedures, and other
expert advice. The primary goal is thus to dispel the mystery surrounding
Lewis acid reagents and to encourage more scientists to use these powerful
synthetic tools to maximum effect. The book contains 14 independently ref
erenced chapters describing a variety of Lewis acids using different metals.
Each metal has different characteristic features of reagent preparation and
practicality which clearly described in that chapter.
I would like to thank Professor K. Ishihara for helping to check parts of the
manuscripts and for useful suggestions. I would also like to express my per
sonal gratitude to all of the invited contributors who carefully honored the
deadlines and thus made the editorial job much easier.
It is my strong hope that this book will be found an invaluable reference
for graduate students as well as chemists at all levels in both academic and
industrial laboratories.
Nagoya H. Y.
October 1998
Contributors

TAKUZO AIDA
Department of Chemistry and Biotechnology, Graduate School of Engineer­
ing, The University of Tokyo, Hongo, Bunkyo, Tokyo 113-8656, Japan
SHIN-ICHI FUKUZAWA
Department of Applied Chemistry, Chuo University, 1113127 Kasuga,
Bunkyo-ku, Tokyo 152, Japan
AKIRA HOSOMI
Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305­
8571,Japan
KAZUAKI ISHIHARA
Research Center for Advanced Waste and Emission Management, Nagoya
University Furo-cho, Chikusa, Nagoya 464-8603, Japan
SHU KOBAYASHI
Graduate School of Pharmaceutical Sciences, The University of Tokyo,
Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
KEIJI MARUOKA
Graduate School of Science, Hokkaido University, Supporo 060-0810, Japan
KOICHI MIKAMI
Department of Chemical Technology, Tokyo Institute of Technology,
Meguro-ku, Tokyo 152, Japan
KATSUKIYO MIURA
Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305­
8571,Japan
YUKIHIRO MOTOYAMA
School of Materials Science, Toyohashi University of Technology, Tempaku­
cho, Toyahashi, 441 Japan
TAKESHI NAKAI
Department of Chemical Technology, Tokyo Institute of Technology,
Meguro-ku, Tokyo 152-8552, Japan
Contributors
HISAONISHIYAMA
School of Materials Science, Toyohashi University of Technology, Tempaku­
cho, Toyohashi 441, Japan
NOBUKl OGUNl
Department of Chemistry, Faculty of Science, Yamaguchi University, 1677-1
Yoshida, Yamaguchi City 753, Japan
MASAYA SAWAMURA
Department of Chemistry, Graduate School of Science, The University of
Tokyo, Hongo, Bunkyo, Tokyo 113, Japan
KEISUKE SUZUKI
Department of Chemistry, Tokyo Institute of Technology, Meguro-ku,
Tokyo 152-8551, Japan
DAISUKETAKEUCHI
Department of Chemistry and Biotechnology, Graduate School of Engineer­
ing, The University of Tokyo, Hongo, Bunkyo, Tokyo 113-8656, Japan
MASAHIRO TERADA
Department of Chemical Technology, Tokyo Institute of Technology,
Meguro-ku, Tokyo 152, Japan
KATSUHIKO TOMOOKA
Department of Chemical Technology, Tokyo Institute of Technology,
Meguro-ku, Tokyo 152-8552, Japan
HISASHI YAMAMOTO
Graduate School of Engineering, Nagoya University Furo-cho, Chikusa,
Nagoya 464-01, Japan
AKIRA YANAGISAWA
Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa,
Nagoya 464-01, Japan
XIV
Contents
List of contributors xiii
1. Introduction i
Hisashi Yamamoto
2. Synthetic utility of bulky aluminium
reagents as Lewis acid receptors 5
Keiji Maruoka
1. Introduction 5
2. Amphiphilic alkylations 6
2.1 Amphiphilic carbonyl alkylations 6
2.2 Amphiphilic conjugate alkylations 10
2.3 Amphiphilic conjugate allylations 12
3. Regio- and stereocontrolled Diels-Alder reaction 15
4. Asymmetric hetero-Diels-Alder reaction 16
5. Claisen rearrangement 21
6. Epoxide rearrangement 23
References 28
Boron reagents 31
Kazuaki Ishihara
1. Introduction 31
2. Arylboron reagents with electron-withdrawing aromatic
group 32
2.1 Tris(pentafluorophenyl)boron as an efficient, air stable, and water-
tolerant Lewis acid catalyst 32
2.2 Diarylborinic acids as efficient catalysts for selective dehydration
of aldols 35
2.3 3,4,5-Trifluorophenylboronic acid as an amidation catalyst 37
3. Chiral boron reagents as Lewis acids 39
3.1 Catalytic enantioselective carbo-Diels-Alder reactions 39
Contents
3.2 Catalytic enantioselective aldol and allylation reactions 51
3.3 Asymmetric reactions of imines mediated by chiral boron reagents 57
References 61
4. Magnesium(II) and other alkali and alkaline
earth metals 65
Akira Yanagisawa
1. Introduction 65
2. Cycloaddition reactions 65
3. Aldol additions, allylations, and other reactions 71
References 74
5. Zinc(II) reagents 77
Nobuki Oguni
1. Introduction 77
2. Scope and limitations 77
References 88
6. Chiral titanium complexes for
enantioselective catalysis 93
Koichi Mikami and Masahiro Terada
1. Introduction 93
2. Carbonyl addition reaction 96
3. Carbonyl-ene reaction 101
4. Asymmetric catalytic desymmetrization 105
5. Kinetic optical resolution 106
6. Positive non-linear effect of non-racemic catalysts 107
7. Enantiomer-selective activation of racemic catalysts 110
8. Ene cyclization 111
9. Aldol reaction 113
10. (Hetero) Diels-Alder reaction 118
11. Cyanohydrine formation 129
12. Miscellaneous reactions 130
Acknowledgements 131
References 131
viii
Contents
7. Tin Lewis acid 137
ShQ Kobayashi
1. Introduction 137
2. Asymmetric aldol reaction 138
2.1 Preparation of chiral tin(II) Lewis acids 138
2.2 Asymmetric aldol reactions of silyl enol ethers derived from acetic
and propionic acid derivatives 138
2.3 Asymmetric synthesis of 2-substituted malate derivatives 140
2.4 Asymmetric synthesis of syn- and anti-1,2 did derivatives 143
2.5 Catalytic asymmetric aldol reactions 147
3. Asymmetric cyanation reaction 151
4. Asymmetric protonation 153
References 155
8. Silicon(IV) reagents 159
Akira Hosomi and Katsukiyo Miura
1. Introduction 159
2. Carbon-oxygen and carbon-nitrogen bond formation 160
3. Carbon—carbon bond formation 161
4. Carbon-hydrogen bond formation 164
References 167
9. Silver and gold reagents i69
Masaya Sawamura
1. Introduction 169
2. Enantioselective aldol reactions of activated isocyanides
and aldehydes 169
3. Enantioselective aldehyde allylation with allyltin reagents
catalysed by a silver(I)-phosphine complex 173
References 175
10. Zr- and Hf-centred Lewis acid in organic
synthesis 177
Keisuke Suzuki
1. Introduction 177
ix