Solid-Phase Organic Syntheses VOLUME SOLID-PHASE PALLADIUM CHEMISTRY Edited by Peter J H Scott, PhD The University of Michigan Ann Arbor, Michigan A JOHN WILEY & SONS, INC., PUBLICATION Solid-Phase Organic Syntheses SOLID-PHASE ORGANIC SYNTHESES Editor-in-Chief Prof Peter J H Scott University of Michigan, Ann Arbor, MI, USA Editorial Advisory Board Prof George Barany University of Minnesota, Minneapolis, MN, USA Prof Dr Stefan Brăase Institute of Organic Chemistry, Karlsruhe, Germany Prof Richard C D Brown University of Southampton, Southampton, UK Prof Anthony W Czarnik University of Nevada, Reno, NV, USA Dr Scott L Dax Galleon Pharmaceuticals, Horsham, PA, USA Prof Ryszard Lazny University of Bialystok, Bialystok, Poland Prof K C Nicolaou The Scripps Research Institute, La Jolla, CA, USA Dr Marcel P´atek Sanofi-Avenits, Tuscon, AZ, USA Prof Alan C Spivey Imperial College, London, UK Dr Patrick G Steel, Ph.D University of Durham, Durham, UK Prof Patrick H Toy University of Hong Kong, Hong Kong, People’s Republic of China Solid-Phase Organic Syntheses VOLUME SOLID-PHASE PALLADIUM CHEMISTRY Edited by Peter J H Scott, PhD The University of Michigan Ann Arbor, Michigan A JOHN WILEY & SONS, INC., PUBLICATION Copyright © 2012 by John Wiley & Sons, Inc All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada 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, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley.com/go/permission 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 No warranty may be created or extended by sales representatives or written sales materials The advice and strategies contained herein may not be suitable for your situation You should consult with a professional where appropriate Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317) 572-4002 Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic formats For more information about Wiley products, visit our web site at www.wiley.com Library of Congress Cataloging-in-Publication Data: Solid-phase palladium chemistry / edited by Peter J H Scott p cm – (Wiley series on solid-phase organic syntheses ; 2) Includes bibliographical references and index ISBN 978-0-470-56665-7 (hardback) Organopalladium compounds Organic compounds—Synthesis Solid-phase synthesis I Scott, Peter J H QD412.P4S65 2012 547 056362–dc23 2011053468 Printed in the United States of America 10 CONTENTS Contributors ix Preface xiii Abbreviations PART I xv INTRODUCTION 1 An Introduction to Solid-Phase Palladium Chemistry Carmen Gil PART II PALLADIUM-MEDIATED SPOS Pd-Catalyzed Solid-Phase Decoration of the 2(1H)-Pyrazinone Scaffold Vaibhav P Mehta and Erik V Van der Eycken One-Step Palladium- and Phenylsilane-Activated Amidation of Solid-Supported Ally Esters Zheming Ruan, Katy Van Kirk, Christopher B Cooper, R Michael Lawrence, and Michael Poss 23 25 35 Solid-Phase Reactions of Polymer-Bound Arenesulfonates with Aryl Grignard Reagents Kwangyong Park and Chul-Hee Cho 41 Fluorous Synthesis of 3-Aminoimidazo[1,2-a]-Pyridine/Pyrazine Library Wei Zhang and Yimin Lu 51 Resin-to-Resin Transfer Reactions (RRTR) via Sonogashira Coupling Judit Tulla-Puche, Rita S Majerle, Fernando Albericio, and George Barany v 59 vi CONTENTS PART III IMMOBILIZED CATALYSTS AND LIGANDS 67 Polymer-supported Palladium Catalysts for Suzuki and Heck Reactions Peter Styring 69 Solid-Phase Catalytic Activity of a Polymer-Supported Palladium Complex Maria M Dell’Anna, Piero Mastrorilli, and Cosimo F Nobile 79 Polyaniline-immobilized Palladium for Suzuki-Miyaura Coupling Reaction in Water Moumita Roy, Pravin R Likhar, and M Lakshmi Kantam 87 10 Synthesis of Polymer-Supported Aryldicyclohexylphosphine for an Efficient Recycling in Suzuki-Miyaura Reactions Katarzyna Glegola and Eric Framery 11 C–C or C–N Reactions Catalyzed by Diadamanthylphosphine Palladium-Based Catalyst Supported on Dab-Dendrimers Karine Heuz´e, Agn´es Fougeret, Julietta Lemo, and Daniel Rosario-Amorin PART IV PALLADIUM-MEDIATED MULTIFUNCTIONAL CLEAVAGE 12 Solid-Phase Reactions of Resin-Supported Boronic Acids Fran¸cois Carreaux, Bertrand Carboni, Herve Deleuze, and Christelle Pourbaix-L’Ebraly 13 A Simple Diversity Linker Strategy Using Immobilized Enol Phosphonates as Electrophiles for Suzuki-Miyaura Reactions Tom M Woods 14 Heck Cleavage of Resin-bound Triazenes Sylvia Vanderheiden, Nicole Jung, and Stefan Brăase 91 97 105 107 119 129 CONTENTS vii 15 Pd-Mediated Cleavage from Tetrafluoroarylsulfonate Linker Units Andrew N Cammidge and Zainab Ngaini 139 16 Palladium-Catalyzed Solid-Phase Synthesis of Allylic Amines Richard C D Brown and Martin L Fisher 145 17 Palladium-Catalyzed Solid-Phase Synthesis of 4-Methylene Pyrrolidines Lynda J Brown, Richard C D Brown, and Martin L Fisher 157 Index 167 154 PALLADIUM-CATALYZED SOLID-PHASE SYNTHESIS OF ALLYLIC AMINES 16 1-(4-Chlorophenyl)prop-2-en-1-ol was synthesized according to the reported procedure [7] 17 Triphenylphosphine (purity ≥98.5%) was purchased from Sigma-Aldrich 18 Diethyl azodicarboxylate (DEAD) is toxic and shock and light sensitive DEAD can explode violently when heated to above 100◦ C It is now difficult to obtain DEAD from commercial sources, and a suitable replacement is diisopropyl azodicarboxylate (DIAD, 95%) obtained from Sigma-Aldrich 19 The formation of the branched regioisomer was supported by gel-phase 13 C NMR data for 1-phenylallyl polystyryl ether 13 C NMR (gel-phase, 75 MHz, CDCl3 ) δ 138.4 (PhCH–), 116.4 (= CH2 ), 81.1 (–CH CH2 ) 20 Tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3 )4 , purity >99%) was purchased from Sigma-Aldrich The same procedure was also applied using an alternative precatalyst system palladium(II) acetylacetonate (0.05 equiv., 99%, Sigma-Aldrich) and 1,2-bis(diphenylphosphino)ethane (0.10 equiv., 99%, Sigma-Aldrich), giving the purified isolated product in 72% yield When the palladium(II) acetylacetonate system was employed, 3,3-di[(E )-3-(4-chlorophenyl)-2-propenyl]-2,4-pentanedione was observed as a by-product 21 Piperidine (purity ≥99.5%) was purchased from Sigma-Aldrich When a single equivalent of a primary amine, such as benzylamine, was used, a substantial amount of diallylated amine (up to 50% of total product) was obtained By using equiv of benzylamine, this side reaction was minimized (