Iron Catalysis in Organic Chemistry
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Iron Catalysis in Organic Chemistry Reactions and Applications Edited by Bernd Plietker Iron Catalysis in Organic Chemistry Edited by Bernd Plietker Related Titles Cornils, B., Herrmann, W. A., Muhler, M., Wong, C.-H. (eds.) Catalysis from A to Z A Concise Encyclopedia 2007 ISBN: 978-3-527-31438-6 Tietze, L. F., Brasche, G., Gericke, K. M. Domino Reactions in Organic Synthesis 2006 SBN: 978-3-527-29060-4 Yudin, A. K. (ed.) Aziridines and Epoxides in Organic Synthesis 2006 ISBN: 978-3-527-31213-9 Cornils, B., Herrmann, W. A., Horvath, I. T., Leitner, W., Mecking, S., Olivier-Bourbigou, H., Vogt, D. (eds.) Multiphase Homogeneous Catalysis 2005 ISBN: 978-3-527-30721-0 Christoffers, J., Baro, A. (eds.) Quaternary Stereocenters Challenges and Solutions for Organic Synthesis 2005 ISBN: 978-3-527-31107-1 Dyker, G. (ed.) Handbook of C-H Transformations Applications in Organic Synthesis 2005 ISBN: 978-3-527-31074-6 Knochel, P. (ed.) Handbook of Functionalized Organometallics Applications in Synthesis 2005 ISBN: 978-3-527-31131-6 Iron Catalysis in Organic Chemistry Reactions and Applications Edited by Bernd Plietker The Editor All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and Prof. Dr. Bernd Plietker publisher do not warrant the information contained Institut für Organische Chemie in these books, including this book, to be free of Universität Stuttgart errors. Readers are advised to keep in mind that Pfaffenwaldring 55 statements, data, illustrations, procedural details or 70569 Stuttgart other items may inadvertently be inaccurate. Germany Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by the Deutsche Nationalbibliothek Die Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available in the Internet at http://dnb.d-nb.de. # 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Typesetting Thomson Digital, Noida, India Printing Strauss GmbH, Mörlenbach Binding Litges & Dopf GmbH, Heppenheim Cover Design Adam-Design, Weinheim Printed in the Federal Republic of Germany Printed on acid-free paper ISBN: 978-3-527-31927-5 V Contents Preface XI List of Contributors XIII 1 Iron Complexes in Organic Chemistry 1 Ingmar Bauer and Hans-Joachim Knölker 1.1 Introduction 1 1.2 General Aspects of Iron Complex Chemistry 2 1.2.1 Electronic Configuration, Oxidation States, Structures 2 1.2.2 Fundamental Reactions 2 1.3 Organoiron Complexes and Their Applications 4 1.3.1 Binary Carbonyl–Iron Complexes 5 1.3.2 Alkene–Iron Complexes 7 1.3.3 Allyl– and Trimethylenemethane–Iron Complexes 8 1.3.4 Acyl– and Carbene–Iron Complexes 9 1.3.5 Diene–Iron Complexes 11 1.3.6 Ferrocenes 18 1.3.7 Arene–Iron Complexes 18 1.4 Catalysis Using Iron Complexes 20 1.4.1 Iron Complexes as Substrates and/or Products in Catalytic Reactions 20 1.4.2 Iron Complexes as Ligands for Other Transition Metal Catalysts 21 1.4.3 Iron Complexes as Catalytically Active Species 21 References 24 2 Iron Catalysis in Biological and Biomimetic Reactions 29 2.1 Non-heme Iron Catalysts in Biological and Biomimetic Transformations 29 Jens Müller 2.1.1 Introduction: Iron in Biological Processes 29 2.1.2 Non-heme Iron Proteins 30 2.1.2.1 Mononuclear Iron Sites 30 VI Contents 2.1.2.2 Dinuclear Iron Sites 39 2.1.3 Summary 45 References 46 2.2 Organic Reactions Catalyzed by Heme Proteins 48 Martin Bröring 2.2.1 Classification and General Reactivity Schemes of Heme Proteins Used in Organic Synthesis 48 2.2.2 Organic Reactions Catalyzed by Cytochromes P450 51 2.2.3 Organic Reactions Catalyzed by Heme Peroxidases 56 2.2.3.1 Dehydrogenations (‘‘Peroxidase Reactivity’’) 56 2.2.3.2 Sulfoxidations (‘‘Peroxygenase Reactivity’’) 57 2.2.3.3 Peroxide Disproportionation (‘‘Catalase Reactivity’’) 58 2.2.3.4 Halogenation (‘‘Haloperoxidase Reactivity’’) 61 2.2.3.5 Epoxidations (‘‘Monoxygenase Activity’’) 62 References 66 3 Iron-catalyzed Oxidation Reactions 73 3.1 Oxidations of C–H and C¼C Bonds 73 Agathe Christine Mayer and Carsten Bolm 3.1.1 Gif Chemistry 73 3.1.2 Alkene Epoxidation 80 3.1.3 Alkene Dihydroxylation 82 3.1.4 The Kharasch Reaction and Related Reactions 84 3.1.5 Aziridination and Diamination 87 References 89 3.2 Oxidative Allylic Oxygenation and Amination 92 Sabine Laschat, Volker Rabe, and Angelika Baro 3.2.1 Introduction 92 3.2.2 Iron-catalyzed Allylic Oxidations 93 3.2.2.1 Simple Iron Salts 93 3.2.2.2 Fe(III) Complexes with Bidentate Ligands 94 þ þ 3.2.2.3 Fe3 /Fe2 Porphyrin and Phthalocyanine Complexes 95 3.2.2.4 Iron(III) Salen Complexes 100 3.2.2.5 Non-heme Iron Complexes with Tetra- and Pentadentate Ligands 100 3.2.3 Oxidative Allylic Aminations 103 3.2.4 Conclusion 107 References 107 3.3 Oxidation of Heteroatoms (N and S) 109 Olga García Mancheño and Carsten Bolm 3.3.1 Oxidation of Nitrogen Compounds 109 Contents VII 3.3.1.1 Oxidation of Hydroxylamines to Nitroso Compounds 109 3.3.1.2 Oxidation of Arylamines 110 3.3.1.3 Other N-Oxidations 110 3.3.2 Oxidation of Sulfur Compounds 111 3.3.2.1 Oxidation of Thiols to Disulfides 111 3.3.2.2 Oxidation of Sulfides 113 3.3.2.3 Oxidative Imination of Sulfur Compounds 119 References 122 4 Reduction of Unsaturated Compounds with Homogeneous Iron Catalysts 125 Stephan Enthaler, Kathrin Junge, and Matthias Beller 4.1 Introduction 125 4.2 Hydrogenation of Carbonyl Compounds 125 4.3 Hydrogenation of Carbon–Carbon Double Bonds 129 4.4 Hydrogenation of Imines and Similar Compounds 136 4.5 Catalytic Hydrosilylations 136 4.6 Conclusion 141 References 142 5 Iron-catalyzed Cross-coupling Reactions 147 Andreas Leitner 5.1 Introduction 147 5.2 Cross-coupling Reactions of Alkenyl Electrophiles 147 5.3 Cross-coupling Reactions of Aryl Electrophiles 154 5.4 Cross-coupling Reactions of Alkyl Electrophiles 161 5.5 Cross-coupling Reactions of Acyl Electrophiles 168 5.6 Iron-catalyzed Carbometallation Reactions 170 5.7 Conclusion 172 References 173 6 Iron-catalyzed Aromatic Substitutions 177 Jette Kischel, Kristin Mertins, Irina Jovel, Alexander Zapf, and Matthias Beller 6.1 General Aspects 177 6.2 Electrophilic Aromatic Substitutions 178 6.2.1 Halogenation Reactions 178 6.2.2 Nitration Reactions 179 6.2.3 Sulfonylation Reactions 180 6.2.4 Friedel–Crafts Acylations 181 6.2.5 Friedel–Crafts Alkylations 183 6.2.5.1 Alkylation with Alcohols, Ethers and Esters 184 6.2.5.2 Alkylation with Alkenes 186 6.3 Nucleophilic Aromatic Substitutions 188 References 191 VIII Contents 7 Iron-catalyzed Substitution Reactions 197 Bernd Plietker 7.1 Introduction 197 7.2 Iron-catalyzed Nucleophilic Substitutions 197 7.2.1 Nucleophilic Substitutions of Non-activated C–X Bonds 197 7.2.1.1 Introduction 197 7.2.1.2 Nucleophilic Substitutions Using Lewis Acidic Fe Catalysts 198 7.2.1.3 Substitutions Catalyzed by Ferrate Complexes 199 7.2.2 Nucleophilic Substitution of Allylic and Propargylic C–X Bonds 202 7.2.2.1 Reactions Catalyzed by Lewis Acidic Fe Salts 202 7.2.2.2 Nucleophilic Substitutions Involving Ferrates 205 7.3 Conclusion 213 References 214 8 Addition and Conjugate Addition Reactions to Carbonyl Compounds 217 Jens Christoffers, Herbert Frey, and Anna Rosiak 8.1 Introduction 217 8.2 Additions to Aldehydes and Ketones 218 8.2.1 Oxygen Nucleophiles 218 8.2.2 Carbon Nucleophiles 219 8.3 Additions to Imines and Iminium Ions 223 8.4 Additions to Carboxylic Acids and Their Derivatives 224 8.4.1 Oxygen Nucleophiles 224 8.4.2 Carbon Nucleophiles 225 8.5 Conjugate Addition to a,b-Unsaturated Carbonyl Compounds 226 8.5.1 Carbon Nucleophiles 226 8.5.1.1 Michael Reactions 226 8.5.1.2 Vinylogous Michael Reactions 230 8.5.1.3 Asymmetric Michael Reactions 232 8.5.1.4 Michael Reactions in Ionic Liquids and Heterogeneous Catalysis 233 8.5.2 Nitrogen Nucleophiles 235 8.6 Synthesis of Heterocycles 236 8.6.1 Pyridine and Quinoline Derivatives 236 8.6.2 Pyrimidine and Pyrazine Derivatives 238 8.6.3 Benzo- and Dibenzopyrans 238 References 239 9 Iron-catalyzed Cycloadditions and Ring Expansion Reactions 245 Gerhard Hilt and Judith Janikowski 9.1 Introduction 245 9.2 Cycloisomerization and Alder–Ene Reaction 245 9.3 [2þ1]-Cycloadditions 249 Contents IX 9.3.1 Iron-catalyzed Aziridine Formation 249 9.3.2 Iron-catalyzed Epoxide Formation 251 9.3.3 Iron-catalyzed Cyclopropane Formation 252 9.4 [2þ2]-Cycloaddition 254 9.5 [4þ1]-Cycloadditions 256 9.6 [4þ2]-Cycloadditions 257 9.6.1 Diels–Alder Reactions with Normal Electron Demand 257 9.6.2 Diels–Alder Reactions with Neutral Electron Demand 259 9.6.3 Diels–Alder Reactions with Inverse Electron Demand 260 9.7 Cyclotrimerization 260 9.8 [3þ2]-Cycloadditions 262 9.9 [3þ3]-Cycloadditions 263 9.10 Ring Expansion Reactions 263 9.11 Conclusion 266 References 266 Index 271 XI Preface Sustainability has emerged as one of the keywords in discussions in the fields of politics, society and science within the past 20 years.