Alkene Metathesis in Organic Synthesis (Topics in Organometallic Chemistry) (Vol 1)

240 Pages·1998·4.5 MB·English

by  Alois Fuerstner

1
Topics in Organometallic Chemistry
Editorial Board:
J.M Brown • P. Dixneuf • A. Fiirstner • L.S. Hegedus
P. Hofmann • P. Knochel • G. van Koten • T.J. Marks
S. Murai • M. Reetz
Topics in Organometallic Chemistry
Forthcoming volumes:
Organometallic Bonding and Ractivity: Fundamental Studies
Volume Editor: J.M. Brown, P. Hofmann
Lanthanides: Chemistry and Use in Organic
Volume Editor: S. Kobayashi
Activation of Unreactive Bonds and Organic Synthesis
Volume Editor: S. Murai
Springer
Berlin
Heidelberg
New York
Barcelona
Budapest
Hong Kong
London
Milan
Paris
Singapore
Tokyo
Alkene Metathesis
in Organic Synthesis
Volume Editor: A. Fiirstner
With contribution by
S.E. Gibson, Y. He, A. Hoveyda, S.P. Keen,
L. Kiessling, N.P. King, M. Mori, K.C. Nicolaou,
J.H. Pawlow, R.R. Schrock, L.E. Strong,
D. Tindall, K.B. Wagener
r
The series Topics in Organometallic Chemistry presents critical overviews of re
search results in organometallic chemistry, where new developments are having a
significant influence on such diverse areas as organic synthesis, pharmaceutical re
search, biology, polymer research and materials science. Thus the scope of coverage
includes a broad range of topics of pure and applied organometallic chemistry. Cov
erage is designed for a broad academic and industrial scientific readership starting
at the graduate level, who want to be informed about new developments of progress
and trends in this increasingly interdisciplinary field. Where appropriate, theoreti
cal and mechanistic aspects are included in order to help the reader understand the
underlying principles involved.
The individual volumes are thematic and the contributions are invited by the vol
umes editors.
In references Topics in Organometallic Chemistry is abbreviated
Top. Organomet. Chem. and is cited as journal
Springer WWW home page: http://www.springer.de
ISSN 1436-6002
ISBN 3-540-64254-4
Springer-Verlag Berlin Heidelberg New York
Library of Congress Cataloging-in-Publication Data
Alkene metathesis in organic synthesis / volume editor, A. Furstner.
p. cm. — (Topics in organometallic chemistry; 1)
Includes bibliographical references.
ISBN 3-540-64254-4 (alk. paper)
I. Alkenes. 2. Ring-opening polymerization. 3. Metathesis (Chemistry)
4. Transition metal catalysts. I. Furstner, Alois.
II. Series.
QD305.H7A45 1998
547'.412-dc21
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Volume Editor
Prof. Alois Furstner
Max-Planck-Institut filr Kohlenforschung
Kaiser-Wilhelm-Platz 1
D-45470 Mulheim an der Ruhr, Germany
e-mail: [email protected]
Editorial Board
Prof. John M. Brown Prof. Pierre Dixneuf
Dyson Perrins Laboratory Campus de Beaulieu
South Parks Road Universite de Rennes 1
Oxford 0X1 3QY, Great Britain Av. du Gl Leclerc
E-mail: [email protected] F-35042 Rennes Cedex, France
[email protected]
Prof. Louis S. Hegedus Prof. Peter Hofmann
Department of Chemistry Organisch-Chemisches Institut
Colorado State University Universitat Heidelberg
Fort Collins, Colorado 80523-1872, USA Im Neuenheimer Feld 270
E-mail: [email protected] D-69120 Heidelberg, Germany
E-mail: [email protected]
Prof. Paul Knochel Prof. Gerard van Koten
Fachbereich Chemie Department of Metal-Mediated Synthesis
Philipps-Universitat Marburg Debye Research Institute
Hans-Meerwein-Strafie Utrecht University
D-35032 Marburg, Germany Padualaan 8
£-ma!7:[email protected] NL-3584 CA Utrecht, The Netherlands
marburg.de E-mail: [email protected]
Prof. Tobin J. Marks Prof. Shinji Murai
Department of Chemistry Faculty of Engineering
Northwestern University Department of Applied Chemistry
2145 Sheridan Road Osaka University
Evanston, Illinois 60208-3113, USA Yamadaoka 2-1, Suita-shi
E-mail: [email protected] Osaka 565, Japan
E-mail: [email protected]
Prof. Manfred Reetz
Max-Planck-Institut fur Kohlenforschung
Kaiser-Wilhelm-Platz 1
D-45470 Mulheim an der Ruhr, Germany
E-mail: [email protected]
Foreword
Organometallic chemistry is a well established research area at the interface of
organic and inorganic chemistry. In recent years this field has undergone a ren
aissance as our understanding of organometallic structure, properties and
mechanism has opened the way for the design of organometallic compounds
and reactions tailored to the needs of such diverse areas as medicine, biology,
materials and polymer sciences and organic synthesis. For example, in the de
velopment of new catalytic processes, organometallic chemistry is helping meet
the challenge to society that the economic and environmental necessities of the
future pose.
As this field becomes increasingly interdisciplinary, we recognize the need for
critical overviews of new developments that are of broad significance. This is our
goal in starting this new series Topics in Organometallic Chemistry.
The scope of coverage includes a broad range of topics of pure and applied or
ganometallic chemistry, where new breakthroughs are being achieved that are of
significance to a larger scientific audience. Topics in Organometallic Chemistry
differs from existing review series in that each volume is thematic, giving an
overview of an area that has reached a stage of maturity such that coverage in a
single review article is no longer possible. Furthermore, the treatment addresses
a broad audience of researchers, who are not specialists in the field, starting at
the graduate student level. Discussion of possible future research directions in
the areas covered by the individual volumes is welcome. Finally, the coverage is
conceptual, focussed and concise, presenting the most significant results and the
underlying principles that are emerging. Thus where appropriate, the authors
are encouraged to include theoretical and mechanistic aspects. Indeed, one of
the first volumes, Organometallic Bonding and Reactivity: Fundamental Stud
ies, edited by John Brown and Peter Hofmann, will be a cornerstone of the series.
It seems appropriate that the first volume of this series, Alkene Metathesis in
Organic Synthesis, edited by Alois Fiirstner, covers one of the most exciting and
dynamic areas of modern organometallic research. Several volumes on other ar
eas, where significant breakthroughs are being achieved, will be published soon.
Furthermore we are convinced that organometallic chemistry is such a fertile
VIII Foreword
and expanding research field that there will be many new topics in the future
that will deserve coverage.
John M. Brown, Oxford
Pierre Dixneuf, Rennes
Alois Fiirstner, Mulheim
Louis S. Hegedus, Fort Collins
Peter Hofmann, Heidelberg
Paul Knochel, Marburg
Tobin J. Marks, Evanston
Shinji Murai, Osaka
Manfred Reetz, Mulheim
Gerard van Koten, Utrecht September 1998
Preface
Olefin metathesis has its roots in polymer chemistry, but it remained a labora
tory curiosity in organic synthesis for decades, simply because most of the early
metathesis catalysts are more or less incompatible with polar functional groups.
The advent of metal alkylidene chemistry completely changed this situation:
various complexes of this type were found to be well defined, single component
(pre)catalysts that are distinguished by a high performance as well as by a re
markable tolerance towards polar groups. The impact of this discovery can
hardly be overestimated: it led to the design of user-friendly tools for all types of
olefin metathesis reactions which, in turn, enable highly imaginative syntheses
of complex target molecules and opened up new vistas for advanced polymer
chemistry and materials science.
This monograph of the new Springer series "Topics in Organometallic Chem
istry" is not intended to provide a comprehensive treatise of metathesis. Even
more so, I guess that such an endeavour would be in vain at the present time due
to the explosive growth in the number of publications, which substantiates the
rapidly increasing importance and popularity of this transformation. However,
the volume collects a series of review articles highlighting some of the most ex
citing advancements that have been reached in recent years. They may enchant
the reader, will serve as a valuable source of information, and hopefully will
stimulate further creative work in this timely field of research. I am indebted to
all fellow chemists who generously contributed their expertise and knowledge to
this project.
Mulheim, September 1998 Alois Furstner
Contents
Olefin Metathesis by Well-Defined Complexes
of Molybdenum and Tungsten
R.R.Schrock 1
Ruthenium-Catalyzed Metathesis Reactions in Organic Synthesis
A. Furstner 37
Ring-Closing Metathesis in the Synthesis of Epothilones
and Polyether Natural Products
K.C.Nicolaou.N.P.King.Y.He 73
Catalytic Ring-Closing Metathesis and the
Development of Enantioselective Processes
A. H. Hoveyda 105
Enyne Metathesis
M.Mori 133
Cross-Metathesis
Susan E. Gibson (n^e Thomas), S. P. Keen 155
Recent Advances in ADMET Chemistry
D.Tindall,J.H.Pawlow,andK.B.Wagener 183
Bioactive Polymers
L. L. Kiessling, LE. Strong 199
Olefin Metathesis by Well-Defined Complexes of
Molybdenum and Tungsten
Richard R. Schrock
Olefin metathesis is a catalytic process whose key step consists of a reaction between an ole-
fin and a transition metal alkylidene complex. Some of the best understood alkylidene cat-
alysts contain Mo or W in its highest possible oxidation state, along with “supporting”
alkoxide ligands and an imido ligand. Recent advances in our understanding of these cata-
lysts from a fundamental perspective, and in ring opening metathesis polymerization
(ROMP) and ring closing metathesis (RCM), in particular, are reviewed.
Keywords: Metathesis, Molybdenum, Tungsten Alkylidene, Ring-opening, Ring-closing.
1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 Methods of Synthesizing Mo and W Alkylidene Complexes. . . . . 5
3 Oxo Alkylidene Complexes . . . . . . . . . . . . . . . . . . . . . . . 7
4 Imido Alkylidene Complexes . . . . . . . . . . . . . . . . . . . . . . 7
5 Variations and Other Types of Alkylidene Complexes. . . . . . . . 12
6 Cross-Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . 16
7 Ring-Opening Metathesis Polymerization (ROMP)
and Other Ring-Opening Reactions . . . . . . . . . . . . . . . . . . 17
8 Conjugated Polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . 22
9 Ring-Closing Metathesis (RCM) . . . . . . . . . . . . . . . . . . . . 23
10 Asymmetric RCM. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
11 Comments and Conclusions. . . . . . . . . . . . . . . . . . . . . . . 30
12 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1
Introduction
Olefin metathesis is a catalytic process whose key step is a reaction between an
olefin and a transition metal alkylidene complex, usually M=CHR (Eq. 1) or M=
CH , in a 2+2 fashion to give an unstable intermediate metalacyclobutane ring
2
[1]. All possible reactions of this general type are reversible, possibly nonpro-
ductive, and in competition with one another, so the overall result depends
heavily on relative rates, and in the case of formation of volatile or insoluble
products, displacement of equilibria as those products form.