Catalytic asymmetric synthesis

853 Pages·2000·50.163 MB·English

by  Iwao Ojima

1 WILEY-VCH
CATALYTIC
ASYMMETRIC
SYNTHESIS
Second Edition
Ch
Catalysts
'OÖÖOr
Edtedby I w ao Ojima
CATALYTIC
ASYMMETRIC
SYNTHESIS
CATALYTIC
ASYMMETRIC
SYNTHESIS
Second Edition
Edited by
IWAO OJIMA
)WILEY-VCH
A John Wiley & Sons, Inc., Publication
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Library of Congress Cataloging-in-Publication Data:
Ojima, Iwao, 1945-
Catalytic asymmetric synthesis / edited by Iwao Ojima.—2nd ed.
p. cm.
Includes index.
ISBN 0-471-29805-0 (alk. paper)
1. Asymmetric synthesis. 2. Catalysis. I. Title.
QD262.035 2000
541.3'9—dc21 99-053574
Printed in the United States of America.
10 9 8 7 6 5 4 3 2 1
CONTENTS
Preface ix
Preface to the First Edition xi
Contributors xiii
1 Asymmetric Hydrogénation 1
Takeshi Ohkuma, Masato Kitamura, and Ryoji Noyori
2 Asymmetric Hydrosilylation and Related Reactions 111
Hisao Nishiyama and Kenji I to h
3 Asymmetric Isomerization of A11 y lamines 145
Susumu Akutagawa and Kazuhide Tani
Chapter 3 Addendum—1999 162
Xin Wen And Iwao Ojima
4 Asymmetric Carbometallations 165
Ei-ichi Negishi
5 Asymmetric Addition and Insertion Reactions of Catalytically-
Generated Metal Carbenes 191
Michael P. Doyle
V
vi CONTENTS
6 Asymmetrie Oxidations and Related Reactions 229
6A Catalytic Asymmetrie Epoxidation of Allylic Alcohols 231
Roy A. Johnson and K. Barry Sharpless
Chapter 6A Addendum—1999 281
Xin Wen and Iwao Ojima
6B Asymmetrie Epoxidation of Unfunctionalized Olefins and
Related Reactions 287
Tsutomu Katsuki
6C Asymmetrie Oxidation of Sulfides 327
Henri B. Kagan
6D Catalytic Asymmetrie Dihydroxylation—Discovery and
Development 357
Roy A. Johnson and K. Barry Sharpless
6E Recent Advances in Asymmetrie Dihydroxylation and
Aminohydroxylation 399
Carsten Bolm, Jens R Hildebrand, and Kilian Muñiz
7 Asymmetrie Carbonylations 429
Kyoko Nozaki and Iwao Ojima
8 Asymmetrie Carbon-Carbon Bond-Forming Reactions 465
8A Asymmetrie Cycloaddition Reactions 467
Keiji Maruoka
8B1 Asymmetric Aldol Reactions—Discovery and Development 493
Masaya Sawamura and Yoshihiko Ito
8B2 Recent Advances in Asymmetric Aldol Addition Reactions 513
ErickM. Carreira
8C Asymmetric Ene Reactions 543
Koichi Mikami and Takeshi Nakai
CONTENTS vii
8D Asymmetrie Michael Reactions 569
Motomu Kanai and Masakatsu Shibasaki
8E Asymmetrie Allylic Alkylation Reactions 593
Barry M. Trost and Chulbom Lee
8F Asymmetrie Cross-Coupling Reactions 651
Masamichi Ogasawara and Tamio Hayashi
8G Asymmetrie Intramolecular Heck Reactions 675
Yariv Donde and Larry E. Overman
9 Asymmetrie Amplification and Autocatalysis 699
Kenso Soai and Takanori Shibata
10 Asymmetrie Phase-Transfer Reactions 727
Martin J. O 'Donneil
11 Asymmetrie Polymerization 757
Yoshio Okamoto and Tamaki Nakano
Epilogue 797
Appendix—List of Chiral Ligands 801
Index 857
PREFACE
The first edition of Catalytic Asymmetric Synthesis, published in the fall of 1993, was very
warmly received by research communities in academia and industries from graduate students,
research associates, faculty, staff, senior researchers, and others. The book was published at the
very moment that the Food & Drug Administration (FDA) in the United States clarified the
situation in "Chiral Drugs," the word "chirotechnology" was created, and chirotechnology
industries were spawning in the United States and Britain.
As accurately predicted in the preface of the first edition, extensive research on new and
effective catalytic asymmetric reactions have been continuing, in an explosive pace, and it is
now obvious that these catalytic asymmetric processes promoted by man-made chiral catalysts
will be the mainstream chemical technology in the 21st century. About five years from the
publication of the original book, there was a clear demand in the synthetic community for an
updated version of this book because advances in the field were accelerated during this period.
Accordingly, I have agreed with the publisher to edit a second edition of this book.
In the second edition, I intended to incorporate all important reaction types that I am aware
of, while keeping the monumental discovery and initial development of certain processes from
the first edition, and highlighting recent advances in this field. The original book had 13 chapters
(9 general-reaction types), which covered most of the important developments at that time.
However, the second edition has 21 chapters (11 general-reaction types) (a total of 21 chapters
for the 21st century is intriguing, isn't it?), reflecting the tremendous expansion in the scope of
catalytic asymmetric synthesis in the past several years. In addition to the nine general-reaction
types covered in the original book, the second edition includes "Asymmetric Carbometallations"
(Chapter 4), "Asymmetric Amplification and Autocatalysis" (Chapter 9), and "Asymmetric
Polymerization" (Chapter 11 ). "Cyclopropanation" in the original book has been replaced with
"Asymmetric Carbene Reactions" (Chapter 5), which now includes powerful asymmetric
intramolecular carbene insertion to C-H bonds. As the Table of Contents shows, there has been
significant expansion and development in the asymmetric carbon-carbon bond-forming reac-
tions (Chapter 8). Thus, this section consists of eight chapters dealing with cycloaddition
reactions, aldol reactions, ene reactions, Michael reactions, allylic substitution reactions,
X PREFACE
cross-coupling reactions, and intramolecular Heck reactions. These processes provide very
useful methods for the highly efficient synthesis of enantio-enriched or enantiopure compounds
of biological, medicinal, agrochemical, and material science related interests.
Once again, the authors of these chapters are all world-leaders in this field, who outline and
discuss the essence of each catalytic asymmetric reaction. Because the separate list of the chiral
ligands in the original book was very well received, a convenient list of the chiral ligands with
citation of relevant references appears in this book as an Appendix.
This book will, once again, serve as an excellent reference book for graduate students as
well as chemists at all levels in both academic and industrial laboratories.
Iwao Ojima
PREFACE TO THE FIRST EDITION
Biological systems, in most cases, recognize a pair of enantiomers as different substances, and
the two enantiomers will elicit different responses. Thus, one enantiomer may act as a very
effective therapeutic drug whereas the other enantiomer is highly toxic. The sad example of
thalidomide is well-known. It is the responsibility of synthetic chemists to provide highly
efficient and reliable methods for the synthesis of desired compounds in an enantiomerically
pure state, that is, with 100% enantiomeric excess (% ee), so that we shall not repeat the
thalidomide tragedy. It has been shown for many pharmaceuticals that only one enantiomer
contains all of the desired activity, and the other is either totally inactive or toxic. Recent
movements of the Food & Drug Administration (FDA) in the United States clearly reflect the
current situation in "Chiral Drugs", that is pharmaceutical industries will have to provide
rigorous justification to obtain the FDA's approval of racemates. Several methods are used to
obtain enantiomerically pure materials, which include classical optical resolution via dias-
tereomers, chromatographic separation of enantiomers, enzymic resolution, chemical kinetic
resolution, and asymmetric synthesis.
The importance and practicality of asymmetric synthesis as a tool to obtain enantiomerically
pure or enriched compounds has been fully acknowledged to date by chemists in synthetic
organic chemistry, medicinal chemistry, agricultural chemistry, natural products chemistry,
pharmaceutical industries, and agricultural industries. This prominence is due to the explosive
development of newer and more efficient methods during the last decade.
This book describes recent advances in catalytic asymmetric synthesis with brief summaries
of the previous achievements as well as general discussions of the reactions. A previous book
reviewing this topic, Asymmetric Synthesis, Vol. 5—Chiral Catalysis, edited by J. D. Morrison,
Academic Press, Inc. (1985), compiles important contributions through 1982. Another book,
Asymmetric Catalysis, edited by B. Bosnich, Martinus Nijhott (1986) also concisely covers
contributions up to early 1984. In 1971, an excellent book, Asymmetric Organic Reactions, by
J. D. Morrison and H. S. Mosher reviewed all earlier important work on the subject and compiled
nearly 850 relevant publications through 1968, including some papers published in 1969. In the
early 1980s, a survey of publications dealing with asymmetric synthesis (in a broad sense)
XI