Indole Ring Synthesis

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3 Indole Ring Synthesis

5 Indole Ring Synthesis From Natural Products to Drug Discovery Gordon W. Gribble Department of Chemistry, Dartmouth College, USA

6 This edition first published John Wiley & Sons, Ltd Registered office John Wiley & Sons, Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 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 the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books. Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book. Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. It is sold on the understanding that the publisher is not engaged in rendering professional services and neither the publisher nor the author shall be liable for damages arising herefrom. If professional advice or other expert assistance is required, the services of a competent professional should be sought. The advice and strategies contained herein may not be suitable for every situation. 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. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall be liable for any damages arising herefrom. Library of Congress Cataloging in Publication Data Names: Gribble, Gordon W. Title: Indole ring synthesis : from natural products to drug discovery / Gordon W. Gribble. Description: Chichester, West Sussex : John Wiley & Sons, Inc., Includes bibliographical references and index. Identifiers: LCCN (print) LCCN (ebook) ISBN (cloth) ISBN (pdf) ISBN (epub) Subjects: LCSH: Organic compounds Synthesis. Indole. Ring formation (Chemistry) Transition metal catalysts. Classification: LCC QD400.5.S95 G (print) LCC QD400.5.S95 (ebook) DDC 661/.816 dc23 LC record available at A catalogue record for this book is available from the British Library. Set in 10/12pt Times by SPi Global, Pondicherry, India

7 Dedicated to the memory of my beloved brother, Alan Paul Gribble,

9 About the Author Gordon W. Gribble is a native of San Francisco, California, and completed his undergraduate education from the University of California at Berkeley in He earned his PhD in organic chemistry from the University of Oregon in 1967, working with Lloyd Dolby on indole chemistry as a National Institutes of Health predoctoral fellow. After his National Cancer Institute postdoctoral fellowship in with Frank Anet at the University of California, Los Angeles, he joined the faculty of Dartmouth College in 1968 where he has been full professor of chemistry since His awards include the National Science Foundation Professional Development Award (1977), the American Cyanamid Academic Award (1988), the Dartmouth College Distinguished Teaching Award (1997), the University of Oregon Chemistry Alumni Achievement Award (1998), Abraham Lincoln High School Wall of Fame (2004), and the Dartmouth College Arts and Sciences Graduate Faculty Mentoring Award (2006). He served as department chair from 1988 to In 2005, he was named to the inaugural endowed chair as The Dartmouth Professor of Chemistry. He has been a visiting scholar/ professor at Caltech; the University of Hawaii; the University of California, Santa Cruz; and Gettysburg College. He is a scientific adviser to the American Council on Science and Health and a member of the editorial boards of Arkivoc and Current Organic Synthesis. Dr. Gribble has published 370 papers on natural product synthesis, synthetic methodology, heterocyclic chemistry, polycyclic aromatic hydrocarbons, natural organohalogen compounds, organic chemical toxicity, and synthetic triterpenoids, one of which entered phase 3 clinical trials for the treatment of chronic kidney disease. He holds 34 patents. Since 1995 he has coedited the annual series Progress in Heterocyclic Chemistry and coauthored the second edition of Palladium in Heterocyclic Chemistry, published in 2007, along with Jack Li. He has written two monographs documenting more than 5000 naturally occurring organohalogen compounds. As a nationally ranked home winemaker for the past 38 years, he has a strong interest in the chemistry of wine and winemaking. He is a rated tournament chess player, enjoys scuba diving, and has a strong personal interest in the battles of Gettysburg and Iwo Jima, to which he has written about. He lives in Lebanon, New Hampshire, with his wife, and has two children, two grandsons, and two stepgrandsons.

11 Preface Given the enormous resurgence in indole ring synthesis over the past decade highlighted by the power of transition metal catalysis there is a need for a comprehensive presentation of the myriad methods for constructing the indole ring: from the ancient to the modern and from the well known to the obscure. The organization that I have adopted follows that in my two earlier reviews on indole ring synthesis, 1,2 beginning with an Introduction on the importance of indoles and their role in society. Given space limitations, with a few exceptions I do not explicitly cover the synthesis of indolines (2,3 dihydroindoles), oxindoles (indolin 2 ones), indoxyls (indole 3 ols), isatins (indoline 2,3 diones), and azaindoles (pyrrolo[2,3 x]pyridines). However, carbazoles, carbolines, and their fused ring derivatives are covered. 1 G.W. Gribble, Contem. Org. Syn., 1994, G.W. Gribble, J. Chem. Soc., Perkin Trans. 1, 2000,

13 Contents 1 Introduction Preview Indole Containing Natural Products Biological Activity of Indoles Indole Containing Pharmaceuticals Indole Containing Materials Indole Containing Ligands Reviews of Indole Ring Synthesis General Reviews on Indole Ring Synthesis Specialized Reviews Name Reactions Miscellaneous Reviews Synthesis of Carbazoles, Carbolines, and Indolocarbazoles Reviews of Indole Analogues 34 References 34 PART I Sigmatropic Rearrangements 39 2 Fischer Indole Synthesis Preview Methods Traditional Methods Metal Catalyzed Methods Solid Phase Fischer Indolization Method Other General Methods Hydrazones Other Variations of Fischer Indole Synthesis Applications of Fischer Indolizations Drug Targets Natural Products Materials General 98 References Gassman Indole Synthesis Bartoli Indole Synthesis Thyagarajan Indole Synthesis Julia Indole Synthesis Miscellaneous Sigmatropic Rearrangements 139

14 xii Contents PART II Nucleophilic Cyclization Madelung Indole Synthesis Wittig Madelung Indole Synthesis Jones Schmid Indole Synthesis Couture Indole Synthesis Wender Indole Synthesis Smith Indole Synthesis Kihara Indole Synthesis Nenitzescu 5 Hydroxyindole Synthesis Engler Kita Indole Synthesis Bailey Liebeskind O Shea Indoline Indole Synthesis Wright Indoline Synthesis Saegusa Indole Synthesis Ichikawa Indole Synthesis Miscellaneous Nucleophilic Cyclizations that Form the Indole Ring Sugasawa Indole Synthesis 244 PART III Electrophilic Cyclization Bischler Indole Synthesis The Nordlander Indole Synthesis Nitrene Cyclization Cadogan Sundberg Indole Synthesis Sundberg Indole Synthesis Hemetsberger Indole Synthesis Taber Indole Synthesis Knochel Indole Synthesis Täuber Carbazole Synthesis 301

15 Contents xiii 32 Quéguiner Azacarbazole Synthesis Iwao Indole Synthesis Hewson Indole Synthesis Magnus Indole Synthesis Feldman Indole Synthesis Butin Indole Synthesis Miscellaneous Electrophilic Cyclizations 317 PART IV Reductive Cyclization Nenitzescu o,β Dinitrostyrene Reductive Cyclization Reissert Indole Synthesis Leimgruber Batcho Indole Synthesis Pschorr Hoppe Indole Synthesis Mąkosza Indole Synthesis Rawal Indole Synthesis The Baeyer Jackson Indole Synthesis and Miscellaneous Reductive Cyclization Indole Syntheses 363 PART V Oxidative Cyclization Watanabe Indole Synthesis Knölker Carbazole Synthesis Miscellaneous Oxidative Cyclizations 396 PART VI Radical Cyclization Fukuyama Indole Synthesis Other Tin Mediated Indole Syntheses The Murphy Indole Synthesis Miscellaneous Radical Promoted Indole Syntheses The Graebe Ullmann Carbazole Carboline Synthesis 424

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