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Polar Organometallic Reagents Polar Organometallic Reagents Synthesis, Structure, Properties and Applications Edited by Andrew E. H. Wheatley University of Cambridge Cambridge, UK Masanobu Uchiyama The University of Tokyo Tokyo, Japan This edition first published 2022 © 2022 John Wiley & Sons Ltd All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions. The right of Andrew E. H. Wheatley and Masanobu Uchiyama to be identified as author(s) of the editorial material in this work has been asserted in accordance with law. Registered Office(s) John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK Editorial Office The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK For details of our global editorial offices, customer services, and more information about Wiley products visit us at www.wiley.com. Wiley also publishes its books in a variety of electronic formats and by print- on- demand. Some content that appears in standard print versions of this book may not be available in other formats. Limit of Liability/Disclaimer of Warranty In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. While the publisher and authors have used their best efforts in preparing this work, they make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. Library of Congress Cataloging- in- Publication Data Names: Wheatley, Andrew E. H, editor. | Uchiyama, Masanobu, editor. Title: Polar organometallic reagents : synthesis, structure, properties and applications / edited by Andrew E. H. Wheatley, University of Cambridge, Cambridge, UK; Masanobu Uchiyama, The University of Tokyo, Tokyo, JP. Description: First edition. | Hoboken, NJ : Wiley, 2022. | Includes bibliographical references and index. Identifiers: LCCN 2021037022 (print) | LCCN 2021037023 (ebook) | ISBN 9781119448822 (hardback) | ISBN 9781119448860 (adobe pdf) | ISBN 9781119448846 (epub) Subjects: LCSH: Organometallic chemistry. Classification: LCC QD411 .P63 2022 (print) | LCC QD411 (ebook) | DDC 547/.05–dc23 LC record available at https://lccn.loc.gov/2021037022 LC ebook record available at https://lccn.loc.gov/2021037023 Cover Design: Wiley Cover Image: © Piotr Zajc/Shutterstock, ANDREW E. H. WHEATLEY Set in 9.5/12.5pt STIXTwoText by Strive, Pondicherry, India 10 9 8 7 6 5 4 3 2 1 v Contents Preface xi List of Contributors xv Acknowledgements xvii 1 The Road to Aromatic Functionalization by Mixed- metal Ate Chemistry 1 Masanori Shigeno, Andrew J. Peel, Andrew E. H. Wheatley, and Yoshinori Kondo 1.1 Introduction 1 1.2 Deprotonation of Aromatics 2 1.2.1 Monometallic Bases 2 1.2.2 Bimetallic Bases 7 1.2.2.1 Group 1/1 Reagents 7 1.2.2.2 Group 1/2 Reagents 11 1.3 Aromatic Ate Complex Chemistry: Metal/Halogen Exchange 13 1.3.1 Introduction 13 1.3.2 Zincates 13 1.3.3 Cuprates 17 1.3.4 Solid- phase Synthesis 24 1.4 Deprotonation Using Ate Complexes 25 1.4.1 Introduction 25 1.4.2 Zincates 26 1.4.3 Cadmates 29 1.4.4 Aluminates 30 1.4.5 Cuprates 32 1.4.6 Argentates 39 1.5 Concluding Remarks 41 References 42 2 Structural Evidence for Synergistic Bimetallic Main Group Bases 49 Robert E. Mulvey and Stuart D. Robertson 2.1 General Introduction 49 2.2 Homometallic Bases 51 2.2.1 Carbanionic Lithium Reagents 51 vi Contents 2.2.2 Heavier Carbanionic Alkali Metal Reagents 56 2.2.3 Alkali Metal Amides 58 2.3 Heterometallic Bases 60 2.3.1 Heteroalkali Metal Bases 60 2.3.2 Alkali Metal Magnesiate Chemistry 64 2.3.3 Early Signs of Synergistic Behaviour in Zincate Chemistry 64 2.3.4 Lithium TMP–Zincate Chemistry 66 2.3.5 Sodium TMP–Zincate Chemistry 73 2.3.6 Lithium Chloride (Turbo Charged) TMP–Zinc Chemistry 78 2.3.7 Indirect TMP Zincation 79 2.3.8 Alkali Metal Group 13 Ates 80 2.3.9 Bimetallic Complexes Without an Alkali Metal Component 85 2.4 Outlook 91 References 91 3 Turbo Charging Group 2 Reagents for Metathesis, Metalation, and Catalysis 97 Michael S. Hill, Anne- Frédérique Pécharman, and Andrew S. S. Wilson 3.1 Introduction and Historical Context: Monometallic s-b lock Reagents and Their Utility 97 3.2 Heterobimetallic Reagents for Selective Metalation 100 3.2.1 Ate Complexes and Superbases 100 3.2.2 Lithium, Sodium, Potassium Magnesiates, MMgX 101 3 3.2.3 Salt Effects and Magnesiate Formation 107 3.2.3.1 ‘Turbo-Grignards’ for Selective Metalation 108 3.2.3.2 Turbo–Hauser Bases 112 3.2.4 Ate Complexes of the Heavier Alkaline Earth Elements Ca, Sr, and Ba 114 3.2.4.1 Alkyl Calciate, Strontiate, and Bariate Derivatives, MM′R3 (M = Li, Na, K; M′ = Ca, Sr, Ba; R = alkyl) 115 3.2.4.2 Alkoxo and Aryloxo Calciate, Strontiate, and Bariate Derivatives, MM′ (OR/Ar)3 (M = Li, Na, K; M′ = Ca, Sr, Ba) 115 3.2.4.3 Amido Calciate, Strontiate, and Bariate Derivatives, MM′(OR/Ar)3 (M = Li, Na, K; M′ = Ca, Sr, Ba) 116 3.3 Homogeneous Catalysis by s- block Reagents 117 3.4 Outlook: Turbo Charging the Turbo Reagents and Prospects for Catalysis 120 References 121 4 Mechanisms in Heterobimetallic Reactivity: Experimental and Computational Insights for Catalyst Design in Small Molecule Activation and Polymer Synthesis 133 Frances N. Singer and Antoine Buchard 4.1 Introduction and Scope of the Chapter 133 4.2 Small Molecule Activation and Catalysis 135 4.2.1 Hydrogen Activation 135 4.2.2 Dinitrogen Activation 147 4.2.3 CO Activation 150 2 4.3 Polymerization Catalysis 152 4.3.1 Olefin polymerization 152 4.3.1.1 Metallocene- based Heterobimetallic Catalysts 154 Contents vii 4.3.1.2 Constrained Geometries Heterobimetallic Catalysts 159 4.3.1.3 Late Transition Metal Heterobimetallic Catalysts 164 4.3.2 Ring- opening Polymerization 171 4.3.2.1 ROP M –O–M Heterobimetallic Catalysts 174 1 2 4.3.2.2 Other Heterobimetallic Catalysts for ROP 178 4.3.3 Ring- opening Copolymerization of Epoxides and Carbon Dioxide 181 4.3.3.1 Mechanistic Insight into Homobimetallic Catalysts 183 4.3.3.2 ROCOP Heterobimetallic Catalysts 186 4.4 Conclusion 192 References 193 5 Cationic Compounds of Group 13 Elements: Entry Point to the p- block for Modern Lewis Acid Reagents 201 Sanjay Singh, Mamta Bhandari, Sandeep Rawat, and Sharanappa Nembenna 5.1 Introduction 201 5.2 General Considerations 202 5.2.1 Classification of Cationic Group 13 Complexes 202 5.2.2 General Methods for the Syntheses of Cationic Group 13 Complexes 203 5.2.3 Characteristics of Counter- anions and Solvents 204 5.2.4 Quantification of LA of Cationic Group 13 Complexes 205 5.2.4.1 Experimental Methods to Quantify Lewis Acidity 206 5.2.4.2 Computational Approaches to Determine Lewis Acidity 207 5.3 Recent Developments in Cationic Group 13 Complexes 209 5.3.1 Advances in the Synthesis and Characterization of Borocations 209 5.3.1.1 Borinium Cations: Two-coordinate Cationic Boron Complexes 209 5.3.1.2 Borenium Cations: Three- coordinate Cationic Boron Complexes 211 5.3.1.3 Borenium Cations Stabilized by NHC and MIC as Neutral C- donor Ligand 212 5.3.1.4 Phosphine- coordinated Borenium Cations 217 5.3.1.5 Borenium Cations Coordinated with N- donor Ligands 218 5.3.1.6 Boronium Cations: Four- coordinate Cationic Boron Complexes 220 5.3.1.7 Miscellaneous Borocations 223 5.3.2 Advances in the Synthesis and Characterization of Aluminium Cations 223 5.3.2.1 Organoaluminium Cations 224 5.3.2.2 Aluminium Cations Supported by N,N′-­donor Monoanionic Bidentate Ligands 230 5.3.2.3 An Aluminium Cationic Complex Supported by a Neutral Bidentate N,N′- donor Ligand 232 5.3.2.4 Miscellaneous Aluminium Cations that Appeared Since 2010 232 5.3.3 Advances in the Synthesis and Characterization of Heavier Group 13 (Ga, In, and Tl) Cations 235 5.3.3.1 Low Oxidation State Univalent Heavier Group 13 Cations (Ga, In, and Tl) 239 5.4 Recent Advancements in Catalytic Applications of Cationic Group 13 Complexes 241 5.4.1 Borocation in Catalysis 241 5.4.1.1 Cationic Boron Complexes in Catalysis 241 5.4.1.2 Hydroboration Reaction 241 5.4.1.3 Hydrosilylation Reaction 243 5.4.1.4 Hydrogenation Reaction 244 5.4.1.5 Use of Chiral NHC 246 viii Contents 5.4.1.6 Use of Chiral Borane 247 5.4.2 Cationic Al Complexes in Catalysis 248 5.4.2.1 Hydroboration Reaction 248 5.4.2.2 Cyanosilylation Reaction 250 5.4.2.3 Hydrosilylation Reaction 252 5.4.2.4 Hydroamination Reaction 254 5.4.2.5 ROP of rac- Lactide, Epoxides and ε- Caprolactone 255 5.4.3 Cationic Heavier Group 13 Complexes in Catalysis 256 5.4.3.1 Cationic Gallium Complexes in Catalysis 256 5.4.3.2 Activation of Alcohols 257 5.4.3.3 Olefin Epoxidation in Water 257 5.4.3.4 Transfer Hydrogenation of Alkene 258 5.4.3.5 Hydroarylation Reaction 258 5.4.3.6 Cycloisomerization of Enyne 260 5.4.3.7 Tandem Carbonyl–Olefin Metathesis 260 5.4.3.8 Polymerization of Propylene Oxide and Isobutylene 261 5.4.3.9 Cationic Indium and Thallium Complexes in Catalysis 262 5.4.3.10 Coupling of Epoxides and Lactones 262 5.4.3.11 ROP of Epoxides, Lactide, and ε- Caprolactone 262 5.5 Concluding Remarks 264 References 265 6 Recent Development in the Solution Structural Chemistry of Main Group Organometallics 271 Alistair M. Broughton, Leonie J. Bole, Andrew E. H. Wheatley, and Eva Hevia 6.1 Introduction 271 6.2 Monometallic Systems 273 6.2.1 Introduction 273 6.2.2 Organo(s- block Metal) Aggregation and Reactivity 273 6.2.3 DOSY on s- block Organometallics 280 6.2.3.1 Development and Early Applications 280 6.2.3.2 Recent Refinements to Diffusion Techniques 283 6.3 Heteropolymetallic Systems 287 6.3.1 Introduction 287 6.3.2 s/s-b lock Systems 287 6.3.2.1 Alkali Metal/Magnesium 287 6.3.2.2 Turbo–Hauser Chemistry 289 6.3.3 s/p-b lock Systems 291 6.3.3.1 Lithium/Aluminium Chemistry and Trans- metal- trapping 291 6.3.3.2 Alkali Metal/Gallium Systems 293 6.3.4 s/d-b lock Systems 294 6.3.4.1 Lithium/Cadmium 294 6.3.4.2 Lithium/Copper 295 6.3.4.3 Alkali Metal/Zinc 302 6.3.4.4 Magnesium/Zinc 308 6.4 Concluding Remarks 311 References 312 Contents ix 7 Chemistry of Boryl Anions: Recent Developments 317 Makoto Yamashita 7.1 Introduction 317 7.2 Boryl Anions as a Salt of Alkali Metals 317 7.2.1 Early Examples of Base- stabilized Boryl Anions and Borylcopper Species 317 7.2.2 Diaminoboryl Anions as a Lithium Salt 318 7.2.3 Base- stabilized Boryl Anion with π- delocalization 321 7.2.3.1 Lewis Base- stabilized Borole Anion 321 7.2.3.2 Carbene- stabilized Boryl Anion 322 7.2.3.3 Stabilization with Cyanide 323 7.2.3.4 Metal- substituted Boryl Anion 325 7.3 Boryl Anions as a Salt of Magnesium, Zinc, and Copper as Relatives of Carbanions 325 7.3.1 Transmetalation of Boryllithium to Magnesium, Copper, and Zinc to Form Borylmetals 325 7.3.2 Transmetalation of Diborane(4) to Magnesium and Zinc to Form Borylmetals 329 7.4 Application of Borylcopper and Borylzinc Species for Synthetic Organic Chemistry 330 7.5 Summary 332 References 333 8 Novel Chemical Transformations in Organic Synthesis with Ate Complexes 337 Keiichi Hirano and Masanobu Uchiyama 8.1 Introduction 337 8.2 Ate Complexes 337 8.3 Di- anion- type Zincate 338 8.3.1 Mono- anion- type Zincates and Di- anion- type Zincates 338 8.3.2 Highly Bulky Di- anion- type Zincate: Li [Znt- Bu ] 339 2 4 8.3.2.1 Halogen–Zinc Exchange in the Presence of Proton Sources 339 8.3.2.2 Anionic Polymerization in Water 340 8.3.3 Cross- coupling Reaction via C–O Bond Cleavage 340 8.4 Heteroleptic Zinc Ate Complexes 342 8.4.1 Deprotonative Metalation of Aromatic C–H Bonds 342 8.4.1.1 Amidozincate Base: Li[(TMP)ZnR ] 343 2 8.4.1.2 Amidoaluminate Base: Li[(TMP)Ali- Bu ] 343 3 8.4.1.3 Amidocuprate Base: Li [(TMP)Cu(CN)R] 345 2 8.4.2 Hydridozincate: M[HZnMe ] 346 2 8.4.3 Silylzincates 348 8.4.3.1 Silylzincation of Alkynes 349 8.4.3.2 Silylzincation of Alkynes via Si–B Activation 350 8.4.3.3 Silylzincation of Alkenes (1): Synthesis of Allylsilanes 350 8.4.3.4 Silylzincation of Alkenes (2): Synthesis of Alkylsilanes 350 8.4.4 Perfluoroalkylzincates Li[R ZnMeCl] and R ZnR 350 F F 8.4.5 Design of Boryl Anion Equivalents and Applications in Synthetic Chemistry 354 8.4.5.1 Borylzincate: M[(pinB)ZnEt ] 355 2 8.4.5.2 Trans- Diboration of Alkynes via pseudo- Intramolecular Activation 357 8.4.5.3 Trans- Alkynylboration of Alkynes 360 8.5 Conclusion 360 References 362 x Contents 9 Isolable Alkenylcopper Compounds: Synthesis, Structure, and Reaction Chemistry 365 Liang Liu, Chao Wang, and Zhenfeng Xi 9.1 Introduction 365 9.2 Well- defined Alkenylcopper Compounds 365 9.2.1 Mono- alkenyl Organocopper Compounds with Intramolecular Coordination 366 9.2.2 Mono- alkenyl Organocopper Compounds Stabilized by N- heterocyclic Carbene 367 9.2.3 Butadienyl Copper Compounds 369 9.3 Summary 379 References 380 Index 383 xi Preface Just as it has done for many years, organometallic and metalloorganic chemistry continues to play a vital role for synthetic chemists in the twenty-f irst century. It offers some of the most effective ways of regiospecifically elaborating organic systems or of harnessing the potential of small mol- ecules. Nevertheless, chemists constantly encounter challenges and target new systems which are not amenable to existing reagents. It is issues such as aggressive nucleophilicity or the implications of temperature instability or solvent sensitivity of many traditional organometallic bases, which have driven much of the research discussed in this volume. A major emergent theme covered is the potential of new, heterobimetallic systems. In particular, the problems of understanding just how reagents predicated on the action of two different metals operate. Synergy vs. cooperativity will be looked at in depth. The new and often unique reactivities of these more complex reagents (or reagent mixtures) and their ability to achieve more effective chemical transformations under increasingly mild condi- tions are discussed. To do this, a broad view of organometallic chemistry is adopted, taking in organooxides, amides and the like as appropriate. Mostly, combinations of main group metals will be looked at but, in particular when considering environmental applications of bimetallic systems, coverage will extend to the d- block. Divided into nine chapters, the volume broadly covers three main fields; structural chemistry in the solid state, understanding often catalytic processes by monitoring reaction pathways, and synthetic applications. The first three chapters are dominated by the role of crystallography in understanding organo- metallic reagents and, in particular, heterobimetallics. Throughout the book, a range of crystal structures are reproduced. For ease, these omit minor disorder, lattice solvent and all but the most chemically relevant hydrogens. Chapter 1 focuses on the work in the laboratory where a new gen- eration of so- called ate or synergic bases were originally developed. The advent of Kondo’s non- nucleophilic zincates is considered and the implications for selective deprotonation are described. The major emphasis then switches to some of the most recent work in this area, where lithium cuprates have been studied and the idea of harnessing the oxidative flexibility of copper in cou- pling chemistry has been developed. If the first chapter shows anything it is that truly understand- ing the nature of many heterobimetallic reagents is vital to predicting or rationalizing their behaviour, and this frequently necessitates crystallographic determination. Chapter 2 focuses on this through the prism of synergistic main group combinations. In particular, a more expansive view of the less strongly polarizing metal component of these systems is considered, enabling the demonstration of some mechanistic variation in formally synergistic systems. This introduces competition between concerted transformations by individually heterobimetallic reagents and stepwise conversions, where new reactivity is enabled in spite of individual steps proceeding through the action of much more traditional reagents that cooperate. Though Chapter 2 tends

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