Remote C-H Bond Functionalizations

1 Cover

2 Title Page Remote C H Bond Functionalizations Methods and Strategies in Organic Synthesis Edited by Debabrata Maiti Srimanta Guin

3 Copyright Editors Debabrata Maiti Indian Institute of Technology Bombay Department of Chemistry Main Gate Rd, IIT Area 400076 Powai, Mumbai India Srimanta Guin Indian Institute of Technology Bombay Department of Chemistry Main Gate Rd, IIT Area 400076 Powai, Mumbai India Cover Cover Image: © selvanegra / Getty Images All books published by Wiley‐VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. 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 The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at < http://dnb.d-nb.de >. © 2021 WILEY‐VCH GmbH, 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, 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. Print ISBN: 978‐3‐527‐34667‐7 ePDF ISBN: 978‐3‐527‐82412‐0 ePub ISBN: 978‐3‐527‐82414‐4 oBook ISBN: 978‐3‐527‐82413‐7

4 1 Introduction

5 2 Transition Metal‐Catalyzed Remote meta ‐C–H Functionalization of Arenes Assisted by meta ‐Directing Templates 2.1 Introduction 2.2 Template‐Assisted meta‐C–H Functionalization 2.3 Mechanistic Considerations 2.4 Conclusion References

6 3 C–H Functionalization of Arenes Under Palladium/Norbornene Catalysis 3.1 Introduction 3.2 Pd(0)‐Catalyzed C–H Functionalization of Aryl (Pseudo)Halides 3.3 Pd(II)‐Catalyzed C–H Functionalization of Arenes 3.4 Conclusions and Outlook Acknowledgments References

7 4 Directing Group Assisted meta ‐C–H Functionalization of Arenes Aided by Norbornene as Transient Mediator 4.1 Introduction 4.2 meta‐C–H Alkylation of Arenes 4.3 meta ‐C–H Arylation of Arenes 4.4 meta ‐C–H Chlorination of Arenes 4.5 meta ‐C–H Amination of Arenes 4.6 meta ‐C–H Alkynylation of Arenes 4.7 Enantioselective meta‐C–H Functionalization 4.8 Conclusion References

8 5 Ruthenium‐Catalyzed Remote C–H Functionalizations 5.1 Introduction 5.2 meta ‐C–H Functionalizations 5.3 para ‐C–H Functionalizations 5.4 meta‐/ortho ‐C–H Difunctionalizations 5.5 Conclusions Acknowledgments References

9 6 Harnessing Non‐covalent Interactions for Distal C(sp 2)–H Functionalization of Arenes 6.1 Introduction 6.2 Non‐covalent Interactions in Metal Catalyzed C H Bond Functionalization 6.3 Overview of Iridium‐Catalyzed Borylation 6.4 Non‐covalent Interactions in Ir‐Catalyzed Borylation 6.5 meta ‐Selective Borylation using Non‐covalent Interactions 6.6 para ‐Selective Borylation using Non‐covalent Interactions 6.7 Conclusions References

10 7 The Non‐directed Distal C(sp 2)–H Functionalization of Arenes 7.1 Introduction 7.2 C–Het Formation 7.3 C C Bond Forming Reactions 7.4 Outlook References Note

11 8 Transition Metal Catalyzed Distal para ‐Selective C–H Functionalization 8.1 Introduction 8.2 Template Assisted para‐Selective C–H Functionalization 8.3 Steric Controlled and Lewis Acid‐Transition Metal Cooperative Catalysis 8.4 Non‐covalent Interaction Induced para‐C–H Functionalization 8.5 Conclusion and the Prospect Acknowledgments References

12 9 Regioselective C–H Functionalization of Heteroaromatics at Unusual Positions 9.1 Introduction 9.2 Indole 9.3 (Benzo)Thiophene 9.4 Pyrrole 9.5 Pyridine 9.6 Miscellaneous Heteroarenes 9.7 Conclusion References

13 10 Directing Group Assisted Distal C(sp 3)–H Functionalization of Aliphatic Substrates 10.1 Introduction 10.2 γ‐C(sp3)–H Functionalization of Aliphatic Acids 10.3 δ‐/ɛ‐C(sp3) H Bond Functionalization of Aliphatic Amines 10.4 γ‐C(sp3) H Bond Functionalization of Aliphatic Ketones or Aldehydes 10.5 γ‐/δ‐C(sp3) H Bond Functionalization of Aliphatic Alcohols 10.6 Conclusions and Outlook References

14 11 Radically Initiated Distal C(sp 3)–H Functionalization 11.1 Introduction 11.2 Distal C(sp3)–H Functionalization Promoted by Carbon‐Centered Radicals 11.3 Distal C(sp 3)–H Functionalization Promoted by Nitrogen‐Centered Radicals 11.4 Oxygen‐Centered Radicals Initiate Distal C(sp3)–H Functionalization 11.5 Summary and Outlook References

15 12 Non‐Directed Functionalization of Distal C(sp 3) H Bonds 12.1 Introduction 12.2 Reactions Occurring Without Formation of Metal–Carbon Bonds 12.3 Reactions Occurring via Formation of Metal–Carbon Bonds 12.4 Altering Innate Reactivity by Polarity Reversal Strategies Acknowledgments References

16 13 Remote Oxidation of Aliphatic C H Bonds with Biologically Inspired Catalysts 13.1 Introduction 13.2 Innate Substrate Based Aspects Governing Site Selectivity in C–H Oxidations 13.3 Remote Oxidations by Reversal of Polarity 13.4 Remote Oxidations Guided by Supramolecular Recognition 13.5 Selective Aliphatic C–H Oxidation at Dicopper Complexes 13.6 Conclusions References

17 Index

18 End User License Agreement

1 Chapter 3 Table 3.1 Bisfunctionalization of aryl (pseudo)halides under Pd(0)/NBE cataly...

2 Chapter 12Table 12.1 Examples of BDEs of aliphatic C H bonds [5].

3 Chapter 13Table 13.1 Catalyst dependent selective oxidation of the androstanediol deriv...Table 13.2 C9 hydroxylation of the androstanediol derivative S2 R.Table 13.3 Oxidation of ibuprofen with the Mn 2 (terpy– COOH)catalyst.Table 13.4 Evidence on favor of a recognition‐driven selectivity.

1 Chapter 2 Scheme 2.1 Directing template assisted meta ‐C H bond functionalization. Rela... Scheme 2.2 Three categories of chelating functionality (CF). (a)