Alkene Metathesis in Organic Synthesis PDF
Preview Alkene Metathesis in Organic Synthesis
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 This work is subject to copyright. All rights are reserved, whether the whole part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosectuion under the German Copyright Law. © Springer-Verlag Berlin Heidelberg 1998 Printed in Germany The use of general descriptive names, registered names, trademarks, etc. in this pub lication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Cover: Friedhelm Steinen-Broo, Pau/Spain; MEDIO, Berlin Typesetting: Data conversion by MEDIO, Berlin spin: 10551906 66/3020-5 4 3 2 1 0 - Printed on acid-free paper. 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.
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