Essential Reagents for Organic Synthesis Essential Reagents for Organic Synthesis Edited by Philip L. Fuchs Purdue University, West Lafayette, IN, USA André B. Charette Université de Montréal, Montréal, Québec, Canada Tomislav Rovis Colorado State University, Fort Collins, CO, USA Jeffrey W. Bode ETH Zürich, Switzerland This edition first published 2016 © 2016 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 www.wiley.com. 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 1988. All rights reserved. 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If professional advice or other expert assistance is required, the services of a competent professional should be sought. Library of Congress Cataloging-in-Publication Data Names: Fuchs, Philip L., 1945- editor. | Charette, A. B. (André B.), 1961- editor. | Rovis, Tomislav, 1968- editor. | Bode, J. W. (Jeffrey W.), editor. Title: Essential reagents for organic synthesis / edited by Philip L. Fuchs, Andre B. Charette, Tomislav Rovis, Jeffrey W. Bode. Description: Chichester, UK ; Hoboken, NJ : John Wiley & Sons, 2016. | Includes index. Identifiers: LCCN 2016021468| ISBN 9781119278306 (paperback) | ISBN 9781119279877 (epub) Subjects: LCSH: Chemical tests and reagents. | Organic compounds–Synthesis. Classification: LCC QD77 .E77 2016 | DDC 547/.2–dc23 LC record available at https://lccn.loc.gov/2016021468 A catalogue record for this book is available from the British Library. ISBN 13: 978-1-119-27830-6 Set in 9½/11½ pt Times Roman by Thomson Press (India) Ltd., New Delhi. Printed and bound in Singapore by Markono Print Media Pte Ltd. e-EROS Editorial Board Editor-in-Chief Philip L. Fuchs Purdue University, West Lafayette, IN, USA Executive Editors André B. Charette Université de Montréal, Montréal, Québec, Canada Tomislav Rovis Colorado State University, Fort Collins, CO, USA Jeffrey W. Bode ETH Zürich, Switzerland Founding Editor Leo A. Paquette The Ohio State University, Columbus, OH, USA Contents Preface ix Pinacolborane 306 Potassium Hexamethyldisilazide 313 Short Note on InChIs and InChIKeys xi Potassium Monoperoxysulfate 334 Potassium tert-Butoxide 353 General Abbreviations xiii Ruthenium(II), Tris(2,2-bipyridine- Bis(dibenzylideneacetone)palladium(0) 2 κN1,κN1 )-, (OC-6-11)- 370 9-Borabicyclo[3.3.1]nonane Dimer 17 Samarium(II) Iodide 378 Boron Trifluoride Etherate 27 Scandium Trifluoromethanesulfonate 388 N-Bromosuccinimide 43 Sodium Azide 398 n-Butyllithium 54 Sodium Borohydride 406 N,N-Carbonyl Diimidazole 72 Sodium Cyanoborohydride 419 Cerium(IV) Ammonium Nitrate 80 Sodium Hexamethyldisilazide 428 m-Chloroperbenzoic Acid 87 Sodium Hydride 438 N-Chlorosuccinimide 98 Sodium Periodate 447 Chlorotrimethylsilane 108 Tetrabutylammonium Fluoride 458 Chlorotris(triphenylphosphine)-rhodium(I) 121 Tetrakis(triphenylphosphine)-palladium(0) 467 (Diacetoxyiodo)benzene 136 Tetra-n-propylammonium Perruthenate 476 Diazomethane 145 p-Toluenesulfonyl Chloride 480 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone 152 Triethylsilane 489 Diisobutylaluminum Hydride 164 Trifluoromethanesulfonic Acid 498 4-Dimethylaminopyridine 170 Trifluoromethanesulfonic Anhydride 507 Dimethyldioxirane 176 Trimethylsilyl Trifluoromethanesulfonate 524 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide Trimethylsilyldiazomethane 543 Hydrochloride 184 Zinc–Acetic Acid 554 N-Iodosuccinimide 188 Iodotrimethylsilane 194 List of Contributors 557 2-Iodoxybenzoic Acid 206 Subject Index 565 Lithium Aluminum Hydride 212 Lithium Diisopropylamide 224 Lithium Naphthalenide 241 Manganese Dioxide 248 Osmium Tetroxide 264 Oxalyl Chloride 283 Oxalyl Chloride–Dimethylformamide 288 Ozone 290 Preface This handbook is a subset of the Encyclopedia of Reagents for • Reagents for Radical and Radical Ion Chemistry Organic Synthesis (EROS), a knowledge base with detailed Edited by David Crich (2009) information on organic-chemical reagents and catalysts. As of mid-2016, the online collection offers reviews on 4959 differ- Data mining of EROS user downloads guided by editorial ent reagents and catalysts that are regularly updated. To keep adjudication has yielded the present collection of 52 often-used up with the continual evolution in the field, about 200 new reagents that will facilitate the daily laboratory endeavor of or updated reagent articles are added per year to the online every organic chemist. The collection contains oxidants (15), database. reductants (10), metal and organic catalysts (11), Brønsted and Lewis acids (8), and bases (6), to cite a few general mechanistic In addition to the complete collection that is available only categories. online (see http://wileyonlinelibrary.com/ref/eros), a number of highly focused single-volume handbooks in print and elec- We hope that this handbook will prove to be an invaluable tronic format on editor-selected subjects have been published primary resource for both beginning graduate students and ex- (Handbook for Reagents in Organic Synthesis, HROS). Recent perienced Ph.D. researchers. titles in the HROS series include: Philip L. Fuchs • Reagents for Organocatalysis Purdue University, West Lafayette, IN, USA Edited by Tomislav Rovis (2016) André B. Charette • Reagents for Heteroarene Functionalization Université de Montréal, Montréal, Québec, Canada Edited by André B. Charette (2015) Tomislav Rovis • Catalytic Oxidation Reagents Colorado State University, Fort Collins, CO, USA Edited by Philip L. Fuchs (2013) Jeffrey W. Bode • Reagents for Silicon-Mediated Organic Synthesis ETH Zürich, Switzerland Edited by Philip L. Fuchs (2011) • Sulfur-Containing Reagents Edited by Leo A. Paquette (2010) Short Note on InChIs and InChIKeys The IUPAC International Chemical Identifier (InChITM) and its print edition of EROS, and all derivative handbooks would compressed form, the InChIKey, are strings of letters represent- find the same information, we appreciate that the strings will ing organic chemical structures that allow for structure search- be of little use to the readers of the print editions, unless they ing with a wide range of online search engines and databases treat them simply as reminders that e-EROS now offers the such as Google and PubChem. While they are obviously an convenience of InChIs and InChIKeys, allowing the online important development for online reference works, such as users to make best use of their browsers and perform searches Encyclopedia of Reagents for Organic Synthesis (e-EROS), in a wide range of media. readers of this volume may be surprised to find printed InChI and InChIKey information for each of the reagents. If you would like to know more about InChIs and InChIKeys, please go to the e-EROS website: www. We introduced InChI and InChIKey to e-EROS in autumn wileyonlinelibrary.com/ref/eros and click on the InChI and 2009, including the strings in all HTML and PDF files. While InChIKey link. we wanted to make sure that all users of e-EROS, the second General Abbreviations Ac acetyl DEAD diethyl azodicarboxylate acac acetylacetonate DET diethyl tartrate AIBN 2,2-azobisisobutyronitrile DIBAL diisobutylaluminum hydride Ar aryl DIEA =DIPEA DIOP 2,3-O-isopropylidene-2,3-dihydroxy-1,4- BBN borabicyclo[3.3.1]nonane bis-(diphenylphosphino)butane BCME dis(chloromethyl)ether DIPEA diisopropylethylamine BHT butylated hydroxytoluene (2,6-di-t-butyl-p- diphos =dppe cresol) DIPT diisopropyl tartrate BINAL-H 2,2-dihydroxy-1,1-binaphthyl-lithium alu- DMA dimethylacetamide minum hydride DMAD dimethyl acetylenedicarboxylate BINAP 2,2-bis(diphenylphosphino)-1,1- DMAP 4-(dimethylamino)pyridine binaphthyl DME 1,2-dimethoxyethane BINOL 1,1-bi-2,2-naphthol DMF dimethylformamide bipy 2,2-bipyridyl dmg dimethylglyoximato BMS borane–dimethyl sulfide DMPU N,N-dimethylpropyleneurea Bn benzyl DMS dimethyl sulfide Boc t-butoxycarbonyl DMSO dimethyl sulfoxide BOM benzyloxymethyl DMTSF dimethyl(methylthio) sulfonium bp boiling point tetrafluoroborate Bs brosyl (4-bromobenzenesulfonyl) dppb 1,4-bis(diphenylphosphino)butane BSA N,O-bis(trimethylsilyl)acetamide dppe 1,2-bis(diphenylphosphino)ethane Bu n-butyl dppf 1,1-bis(diphenylphosphino)ferrocene Bz benzoyl dppp 1,3-bis(diphenylphosphino)propane DTBP di-t-butyl peroxide CAN cerium(IV) ammonium nitrate Cbz benzyloxycarbonyl EDA ethyl diazoacetate CDI N,N -carbonyldiimidazole