Edited by A. Stephen K. Hashmi and Dean F. Toste Modern Gold Catalyzed Synthesis Edited by A. Stephen K. Hashmi and F. Dean Toste Modern Gold Catalyzed Synthesis Further Reading Mohr, F. (ed.) Ertl, G., Knözinger, H., Schüth, F., Gold Chemistry Weitkamp, J. (eds.) Highlights and Future Directions Handbook of Heterogeneous 2009 Catalysis ISBN: 978-3-527-32086-8 8 Volumes 2008 Laguna, A. (ed.) ISBN: 978-3-527-31241-2 Modern Supramolecular Gold Chemistry Ding, K., Uozumi, Y. (eds.) Gold-Metal Interactions and Applications Handbook of Asymmetric 2008 Heterogeneous Catalysis 2008 ISBN: 978-3-527-32029-5 ISBN: 978-3-527-31913-8 Dupont, J., Pfeffer, M. (eds.) Palladacycles Synthesis, Characterization and Applications 2008 ISBN: 978-3-527-31781-3 Edited by A. Stephen K. Hashmi and F. Dean Toste Modern Gold Catalyzed Synthesis Wiley-VCH The Editors All books published by are carefully produced. Nevertheless, authors, editors, and pub- Prof. Dr. A. Stephen K. Hashmi lisher do not warrant the information contained in Organisch-Chemisches Institut these books, including this book, to be free of errors. Universität Heidelberg Readers are advised to keep in mind that statements, Im Neuenheimer Feld 270 data, illustrations, procedural details or other items 69120 Heidelberg may inadvertently be inaccurate. Library of Congress Card No.: applied for Prof. F. Dean Toste Department of Chemistry British Library Cataloguing-in-Publication Data University of California A catalogue record for this book is available from the Berkeley, CA 94720-1460 British Library. USA Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publica- tion in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de. # 2012 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, micro- film, or any other means – nor transmitted or trans- lated 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. Print ISBN: 978-3-527-31952-7 ePDF ISBN: 978-3-527-64689-0 ePub ISBN: 978-3-527-64688-3 mobi ISBN: 978-3-527-64687-6 oBook ISBN: 978-3-527-64686-9 Cover Design Formgeber, Eppelheim Typesetting Thomson Digital, Noida, India Printing and Binding betz-druck GmbH, Darmstadt, Germany V Contents List of Contributors XIII 1 Hydrochlorination of Acetylene Catalyzed by Gold 1 Marco Conte and Graham J. Hutchings 1.1 Introduction 1 1.2 Reactions of Alkynes Using Gold Chloride as Catalyst 2 1.3 The Correlation of E 88 with the Activity of Gold for the Hydrochlorination of Acetylene 4 1.3.1 The Initial Correlation 4 1.3.2 Conceptual Developments of the E8 Correlation 5 1.3.3 Further Study of the Correlation of E8 with the Activity of Platinum Group Metals 8 1.3.4 The E8 Correlation Applied to Homogeneous and Nonhomogeneous Gold Nanoalloys 9 þ 1.4 Central Role of Au3 and Regeneration of Au/C Catalysts 12 1.5 Reaction Mechanism of Alkynes Over Au/C Catalysts 14 1.5.1 Effect of the Individual Components of the Reactants to Au/C 14 1.5.2 Reaction of Higher Alkynes Over Au/C 16 1.5.3 Hydrochlorination of 1-hexyne, phenylacetylene, and 2-hexyne Over Au/C Catalyst 17 1.5.4 Computational Studies of the Reaction of Acetylene Over Au/C 21 1.6 Chemical Origin of the E8 Correlation and General Remarks 22 1.7 Commercial Processes and Economic Aspects of Vinyl Chloride Monomer Manufacture 24 References 25 2 Gold-Catalyzed Reduction Reactions 27 Avelino Corma and Pedro Serna 2.1 Introduction 27 2.2 Hydrogenation of Multiple C¼C Bonds. Role of the Gold Oxidation State 28 2.2.1 Introduction 28 VI Contents 2.2.2 First Solid Gold Catalysts: from Extended Au Surfaces to Highly Dispersed Nanoparticles 28 2.2.3 Recent Advances in Supported Gold Chemistry: from Highly Dispersed Nanoparticles to Individual Supported Au Atoms 31 2.2.4 Summary 34 2.3 Hydrogenation of a,b-Unsaturated Aldehydes 34 2.3.1 Introduction 34 2.3.2 Chemistry of Gold Nanoparticles: First Studies and Hypotheses 36 2.3.3 Strong Metal–Support Interactions: Effect of Electronic Transfers and Decoration on the Gold Nanoparticles 37 2.3.4 Effect of Morphological Factors: Size and Shape 38 2.3.5 Summary 39 2.4 Hydrogenation of Substituted Nitroaromatic Compounds 41 2.4.1 Introduction 41 2.4.2 Gold Catalysts for the Production of Substituted Nitro Compounds 42 – 2.4.3 Hydrogenation of NO2 Groups on Gold Catalysts: Reaction Pathway 43 2.4.4 Chemoselectivity of Gold Catalysts for the Hydrogenation 47 of NO2 groups 2.4.5 Activity of Gold Catalysts for the Hydrogenation of NO2 groups 49 2.4.6 Summary 51 References 51 3 Gold-Catalyzed Benzannulations: Asao–Yamamoto Benzopyrylium Pathway 55 Naoki Asao and Yoshinori Yamamoto 3.1 Introduction 55 3.2 Acetylenic Compounds as 2p Systems 56 3.3 Enols as 2p Systems 60 3.4 Enol Ethers as 2p Systems 62 3.5 Benzynes as 2p Systems 63 3.6 Synthesis of Phthalazine Derivatives 64 3.7 Application to the Synthesis of Angucyclinone Antibiotics and Other Applications in Total Synthesis 65 3.8 Copper-Catalyzed Benzannulations 67 3.9 Conclusion 68 References 69 4 Gold-Catalyzed Reactions of Propargyl Esters, Propargyl Alcohols, and Related Compounds 75 Pablo Mauleon and F. Dean Toste 4.1 Introduction and Extent of This Chapter 75 4.2 Propargyl Esters 76 Contents VII 4.2.1 General Mechanistic Considerations 76 4.2.1.1 [2,3]- and [3,3]-Rearrangements 77 4.2.1.2 Reversibility 78 4.2.1.3 Ionization 80 4.2.1.4 Double [2,3]-Rearrangements 83 4.2.2 Reactions Initiated by [2,3]-Rearrangements 85 4.2.2.1 The Rautenstrauch Rearrangement 86 4.2.2.2 Alkene Cyclopropanations 87 4.2.2.3 Enantioselective Transformations After [2,3]-Rearrangements 92 4.2.2.4 Nucleophilic Attack on Gold Carbenoids Generated After [2,3]-Rearrangements 94 4.2.3 Reactions Initiated by [3,3]-Rearrangements 96 4.2.3.1 Nucleophilic Double Bonds 97 4.2.3.2 Triple Bonds 99 4.2.3.3 Aromatic Groups 100 4.2.3.4 Alkyl Groups 100 4.2.3.5 Heteroatoms 102 4.2.3.6 Electrophilic Trapping of Vinyl–Gold Intermediates 103 4.2.3.7 Other Processes 104 4.3 Propargyl Ethers 107 4.3.1 Propargyl Vinyl Ethers 107 4.3.2 Propargyl Alkyl Ethers 110 4.3.3 Other Ether Substitution Patterns 113 4.4 Propargyl Alcohols 115 4.4.1 Alkyne Hydration 115 4.4.2 Meyer–Schuster Rearrangements 115 4.4.3 Nucleophilic Substitution at the Propargylic Position 117 4.4.4 Ring Expansions 117 4.4.5 Other Reactions Involving Propargyl Alcohols 119 4.5 Propargyl Amines 121 4.6 Propargyl Carbonates, Amides, and Carbamates 124 4.7 Other Propargyl Substitution Patterns 127 4.8 Conclusion 129 References 130 5 Intramolecular Hydroarylation of Alkynes 135 Paula de Mendoza and Antonio M. Echavarren 5.1 Introduction 135 5.2 Intramolecular Reactions of Arenes with Alkynes 137 5.3 Intramolecular Reactions of Electron-Rich Heteroarenes with Alkynes 142 5.4 Conclusion and Outlook 148 References 148 VIII Contents 6 Gold–Alkyne Complexes 153 Maria Agostina Cinellu 6.1 Introduction 153 6.2 Description of the M–p-Bond Interaction in Alkene and Alkyne Complexes 154 6.3 Gold(0) Complexes 155 6.4 Gold(I) Complexes 155 6.4.1 Neutral Derivatives 155 6.4.2 Cationic Derivatives 158 6.4.3 p-Complexation of Gold(I) at Metal–Alkynyl Units M–CC–R 164 6.5 Gold(III) complexes 167 6.6 Theoretical Studies 167 References 171 7 Gold–Alkene Complexes 175 Maria Agostina Cinellu 7.1 Introduction 175 7.2 Gold(0) Derivatives 176 7.3 Gold(I) Complexes 176 7.3.1 Neutral Derivatives 176 7.3.1.1 14-Electron Species 176 7.3.1.2 16-Electron Species 178 7.3.2 Cationic Derivatives 181 7.3.2.1 14-Electron Species 181 7.3.2.2 16-Electron Species 186 7.4 Gold(III) Complexes 191 7.5 Theoretical Studies 192 References 196 8 Hydration and Hydroalkoxylation of CC Multiple Bonds 201 J. Henrique Teles 8.1 Historical Perspective 201 8.1.1 Addition of Water to Alkynes 201 8.1.2 Addition of Alcohols to Alkynes 202 8.2 Gold Catalysts 202 8.2.1 First Reports of Gold Catalysts 203 8.2.2 The Discovery of Au(I) Catalysts 204 8.2.2.1 Catalyst Precursors 206 8.2.2.2 The Importance of Chemical Equilibria 208 8.3 Hydration and Hydroalkoxylation of CC Triple Bonds (Alkynes) 209 8.3.1 Effect of Alcohol Structure 209 8.3.2 Addition of Water to Alkynes 211 8.3.3 Addition of Alcohols to Simple Alkynes 215 8.3.4 Reactions Involving Propargylic Alcohols 217 8.3.5 Additions to Homopropargylic Alcohols and Other Alkynols 220 Contents IX 8.3.6 Reactions Involving Propargylic Ethers 224 8.4 Hydration and Hydroalkoxylation of CC Double Bonds (Allenes and Alkenes) 226 8.4.1 Addition of Alcohols to Allenes 226 8.4.2 Cyclization of Allenyl and Propargyl Ketones 227 8.4.3 Addition of Alcohols to Alkenes 230 References 234 9 Gold-Catalyzed Aldol and Related Reactions 237 Christoph Hubbert and A.