Helmut Werner Gerhard Erker (Eds.) Organometallics in Organic Synthesis 2 Aspects of a Modern Interdisciplinary Field Contributors: F. Bickelhaupt, H. Brunner, A. de Meijere, R. Gleiter, W.D. Jones, Th. Kauffmann, A. Nakamura, H.-U. ReiBig, A. Salzer, K. Schlagl, H. Schwarz, G. Suss-Fink, H. tom Dieck, H. Vahrenkamp, P. Vogel, G. Wilke, U. Zenneck With 223 Figures and Schemes and 11 Tables Springer-Verlag Berlin Heidelberg New York London Paris Tokyo Hong Kong Prof. Dr. Helmut Werner Institut fur Anorganische Chemie der Universitat Wurzburg Am Hubland, D-8700 Wurzburg Prof. Dr. Gerhard Erker Institut fur Organische Chemie der Universitat Wiirzburg Am Rubland, D-8700 Wiirzburg Proceedings of the Second Symposium on "Organic Synthesis via Organometallics" Wiirzburg/FRG,19.-22.1O.1988 Sponsored by the Stiftung Volkswagenwerk, Hannover, FRG ISBN -13 :978-3-540-50531-0 e-ISBN -13 :978-3-642-74 269-9 DOl: 10.1007/978-3-642-74269-9 This work is subject to copyright. 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This infonnation can be obtained from the instructions on safe laboratory practice and from the manufacturers of chemicals and laboratory equipment. 2152/3140-543210-Printed on acid-free paper Preface Organometallic chemistry had its origins and its first period of recognition in relation to organic synthesis in the last century. Starting with the exciting work of Frankland and confirmed by the even more impressive investigations of Grignard, organometallic compounds became v1ell established being of considerable value to the organic chemist. Later, the use of organolithium and organoaluminium reagents, mainly developed by Wittig and Ziegler in the middle of this century, received wide-spread attention. The importance of organotransition-metal complexes as reagents or catalysts in organic synthesis was a more recent discovery. Following some pioneering work carried out in Europe, the United States and Japan, various research groups throughout the world have found new applications for the steadily growing number of organometallic compounds, particularly of the transition metals. To streamline these efforts, the "Volkswagen Stiftung", which from the very beginning supported research in newly developing areas, initiated in 1986 a new programme entitled "Organic Synthesis via Organometallics". Already in its first year this has turned out to be a great success. The enthusiasm and the continuing interest among academic and industrial chemists led to a first symposium in Hamburg in February 1987 which was found to be a great stimulus for most of the participants. To retain this momentum, the authorities of the "Volkswagen Stiftung" spontaneously agreed to sponsor a second symposium which was held in Wlirzburg in October 1988. During three days, eighteen main lectures were presented by VI distinguished scientists from Germany and abroad covering various aspects of this interdisciplinary field. Almost all of the contributions are collected in this volume which hopefully will stimulate new ideas and further cooperation between chemists from different areas. Our special thanks go to the authors for their willingness to submit a manuscript and for their collaboration in this endeavor. Wurzburg, 30. Marz 1989 Helmut Werner Gerhard Erker ~ist of contributors Prof. Dr. Friedrich Bickelhaupt, Scheikundig Laboratorium, Vri je Universiteit Amsterdam, De Boelelaan 1083, NL-1081 HV Amsterdam Prof. Dr. Henri Brunner, Insti tut fur Anorganische Chemie der Universitat Regensburg, UniversitatsstraBe 31, 0-8400 Regensburg Prof. Dr. Armin de Meijere, Institut fur Organische Chemie der Universitat Hamburg, Martin-Luther-King-Platz 6, 0-2000 Hamburg 13 Prof. Dr. Rolf Gleit er, Organisch-Chemisches Insti tut der Universitat Heidelberg, Im Neuenheimer Feld 270, 0-6900 Heidelberg· Prof. Dr. William D. Jones, Department of Chemistry, University of Rochester, River Station, Rochester, New York 14627, USA Prof. Dr. Thomas Kauffmann, Organisch-Chemisches Institut, Westfalische Wilhelms-Universitat Munster, CorrensstraBe 40, 0- 4400 Munster Prof. Dr. Akira Nakamura, Department of Macromolecular Science, Faculty of Science, Osaka University, Toyonaka, Osaka 560, Japan Prof. Dr. Hans-Ulrich ReiBig, Institut fur Organische Chemie, Technische Hochschule Darmstadt, PetersenstraBe 22, 0-6100 Darmstadt Priv . Doz. Dr. Albrecht Salzer, Anorganisch-Chemisches Insti tut der Universitat Zurich, WinterthurerstraBe 190, CH-8057 Zurich Prof. Dr. Karl Schlagl, Institut fur Organische Chemie der Universitat Wien, Wahringer StraBe 38, A-1090 Wien 9 Prof. Dr. Helmut Schwarz, Technische Universitat Berlin, Institut fur Organische Chemie, StraBe des 17. Juni 135, 0-1000 Berlin 12 VIII Prof. Dr. Georg Suss-Fink, Institut de Chimie, Universite de Neuchatel, Avenue de Bellevaux 51, CH-2000 Neuchatel Prof. Dr. Heindirk tom Dieck, Institut fur Anorganische und Angewandte Chemie der Universitat Hamburg, Martin-Luther-King Platz 6, 0-2000 Hamburg 13 Prof. Dr. Heinrich Vahrenkamp, Institut fur Anorganische und Analytische Chemie, Albert-Ludwigs-Universitat Freiburg, AlbertstraBe 21, 0-7800 Freiburg Prof. Dr. Pierre Vogel, Insti tut de Chimie Organique, Univ ersi te de Lausanne, Rue de la Barre 2, CH-1005 Lausanne Prof. Dr. GUnther Wilke, Max-Planck-Institut fur Kohlenforschung, Kaiser-Wilhelm-Platz 1, 0-4330 Mulheim a. d. Ruhr Dr. Ulrich Zenneck, Anorganisch-Chemisches Institut der Universitat Heidelberg, Im Neuenheimer Feld 270, 0-6900 Heidelberg CON TEN T S Page G. Wilke Organic Syntheses via Organometallics 1 H. tom Dieck*, C. Munz and J. Ehlers Diazadiene-Controlled C-C Coupling Reactions on 21 Palladium and Iron D. Hu, H. Pritzkow, H. Schaufele, C. Tolxdorff, and U. Zenneck* Highly Reactive x-Arene Iron Complexes and Their Use in 45 Stoichiometric and Catalytic Cyclic Addition Reactions K. Schlogl Stereochemistry of Arenetricarbonylchromium Complexes - 63 Useful Intermediates for Stereoselective Syntheses P. vogel* and R. Roulet Ironcarbonyl Complexes of Exocyclic Polyenes. The 79 Tricarbonyl(1,3-diene)iron Moiety as Remote Substituent R. Gleiter*, M. Karcher, D. Kratz, S. Rittinger and V. Schehlmann Metal-Induced Dimerisations of Cyclic Diacetylenes 109 G. SUss-Fink Novel Catalytic Applications of Ruthenium Clusters 127 A. Nakamura* and H. Yasuda Selective Organic Synthesis by Diene Complexes of Early 137 Transition Metals F. Bickelhaupt Metallacyclobutanes: Synthons and Catalysts 145 x Th. Kauffmann New Properties of Reagents by Complexation of Carbanions 161 on Transition-Metals: Which Metal is in Each Case the Most Favorable One? W. D. Jones*, V. L. Chandler, R. P. Duttweiler, Jr., F. J. Feher, E. T. Hessell, G. C. Hsu and W. P. Kosar Organometallic Transformations via C-H Bond Activation 185 G. Czekay, T. Drewello, K. Eller, C. B. Lebrilla, T. Prusse, C. Schulze, N. Steinruck, D. Sulzle, T. Weiske and H. Schwarz* Remote Functionalization of Carbon-Hydrogen and Carbon- 203 Carbon Bonds by Bare Transition Metal Ions in the Gas Phase H. Vahrenkamp Aktivierung von Mehrfachbindungssystemen auf Clustern 235 A. de Meijere*, A. Kaufmann, R. Lackmann, H.-C. Militzer, O. Reiser, S. Schomenauer and A. Weier Directed - and Undirected - Syntheses of Novel Organic 255 Compounds via Iron, Cobalt and Chromium Complexes H. Brunner Enantioselective Synthesis of Organic Compounds with 277 Optically Active Transition Metal Catalysts and Transition Metal Compounds A. Salzer Diolefin Iron Complexes - Useful and Versatile Tools in 291 Organic Synthesis R. U. ReiBig Donor-Acceptor-Substituted Cyclopropanes via Fischer 311 Carbene Complexes ORGANIC SYNTHESES VIA ORGANOMETALLICS G. Wilke Max-Planck-Instiut fUr Kohlenforschung Kaiser-Wilhelm-Platz 1. 4330 Mulheim an der Ruhr. FRG In 1890 Mond. Lange and Quinkel) discovered the synthesis of Ni(CO)4 from metallic nickel and carbon monoxide. A few years later Sabatier and Senderens2) were led to attempt the preparation of a volatile compound similar to Ni[COI4 using ethene instead of carbon monoxide. but without success. Nevertheless, in the course of these experiments they discovered catalytic hydrogenation. More than 60 years later we were able to realize the original idea of Sabatier in part when we managed to prepare first Ni[CODI/) and later Ni[C2H4134). Numerous complexes of nickel(O) have since been synthesized. Today I would like to describe the application of nickel complexes in stoichiometric as well as in catalytic reactions. Cyclooligomerizations of unsaturated substrates mediated by nickel(O) are characterized by the very general phenomena of oxidative addition and reductive elimination. The following example represents these types of reactionS). j- coo - 85'/. H. Werner and G. Erker (Eds.) Organometallics in Organic Synthesis 2 © Springer-Verlag Berlin Heidelberg 1989