General Abbreviations Ac acetyl DIEA =DIPEA acac acetylacetonate DIOP 2,3-O-isopropylidene-2,3-dihydroxy-1,4- AIBN 2,2-azobisisobutyronitrile bis-(diphenylphosphino)butane Ar aryl DIPEA diisopropylethylamine diphos =dppe BBN borabicyclo[3.3.1]nonane DIPT diisopropyl tartrate BCME dis(chloromethyl)ether DMA dimethylacetamide BHT butylated hydroxytoluene (2,6-di-t-butyl-p- DMAD dimethyl acetylenedicarboxylate cresol) DMAP 4-(dimethylamino)pyridine BINAL-H 2,2-dihydroxy-1,1-binaphthyl-lithium alu- DME 1,2-dimethoxyethane minum hydride DMF dimethylformamide BINAP 2,2-bis(diphenylphosphino)-1,1- dmg dimethylglyoximato binaphthyl DMPU N,N-dimethylpropyleneurea BINOL 1,1-bi-2,2-naphthol DMS dimethyl sulfide bipy 2,2-bipyridyl DMSO dimethyl sulfoxide BMS borane–dimethyl sulfide DMTSF dimethyl(methylthio) sulfonium Bn benzyl tetrafluoroborate Boc t-butoxycarbonyl dppb 1,4-bis(diphenylphosphino)butane BOM benzyloxymethyl dppe 1,2-bis(diphenylphosphino)ethane bp boiling point dppf 1,1-bis(diphenylphosphino)ferrocene Bs brosyl (4-bromobenzenesulfonyl) dppp 1,3-bis(diphenylphosphino)propane BSA N,O-bis(trimethylsilyl)acetamide DTBP di-t-butyl peroxide Bu n-butyl Bz benzoyl EDA ethyl diazoacetate EDC 1-ethyl-3-(3-dimethylaminopropyl)- CAN cerium(IV) ammonium nitrate carbodiimide Cbz benzyloxycarbonyl EDCI =EDC CDI N,N -carbonyldiimidazole ee enantiomeric excess CHIRAPHOS 2,3-bis(diphenylphosphino)butane EE 1-ethoxyethyl Chx =Cy Et ethyl cod cyclooctadiene ETSA ethyl trimethylsilylacetate cot cyclooctatetraene EWG electron withdrawing group Cp cyclopentadienyl CRA complex reducing agent Fc ferrocenyl CSA 10-camphorsulfonic acid Fmoc 9-fluorenylmethoxycarbonyl CSI chlorosulfonyl isocyanate fp flash point Cy cyclohexyl Hex n-hexyl d density HMDS hexamethyldisilazane DABCO 1,4-diazabicyclo[2.2.2]octane HMPA hexamethylphosphoric triamide DAST N,N-diethylaminosulfur trifluoride HOBt l-hydroxybenzotriazole dba dibenzylideneacetone HOBT =HOBt DBAD di-t-butyl azodicarboxylate HOSu N-hydroxysuccinimide DBN 1,5-diazabicyclo[4.3.0]non-5-ene DBU 1,8-diazabicyclo[5.4.0]undec-7-ene DCC N,N-dicyclohexylcarbodiimide Im imidazole (imidazolyl) DCME dichloromethyl methyl ether Ipc isopinocampheyl DDO dimethyldioxirane IR infrared DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone de diastereomeric excess KHDMS potassium hexamethyldisilazide DEAD diethyl azodicarboxylate DET diethyl tartrate LAH lithium aluminum hydride DIBAL diisobutylaluminum hydride LD50 dose that is lethal to 50% of test subjects LDA lithium diisopropylamide PMDTA N,N,N,N,N-pentamethyldiethylene- LDMAN lithium 1-(dimethylamino)naphthalenide triamine LHMDS =LiHMDS PPA polyphosphoric acid LICA lithium isopropylcyclohexylamide PPE polyphosphate ester LiHMDS lithium hexamethyldisilazide PPTS pyridinium p-toluenesulfonate LiTMP lithium 2,2,6,6-tetramethylpiperidide Pr n-propyl LTMP =LiTMP PTC phase transfer catalyst/catalysis LTA lead tetraacetate PTSA p-toluenesulfonic acid lut lutidine py pyridine RAMP (R)-1-amino-2-(methoxymethyl)pyrrolidine m-CPBA m-chloroperbenzoic acid rt room temperature MA maleic anhydride MAD methylaluminum bis(2,6-di-t-butyl-4- salen bis(salicylidene)ethylenediamine methylphenoxide) SAMP (S)-1-amino-2-(methoxymethyl)pyrrolidine MAT methylaluminum bis(2,4,6-tri-t- SET single electron transfer butylphenoxide) Sia siamyl (3-methyl-2-butyl) Me methyl MEK methyl ethyl ketone TASF tris(diethylamino)sulfonium MEM (2-methoxyethoxy)methyl difluorotrimethylsilicate MIC methyl isocyanate TBAB tetrabutylammonium bromide MMPP magnesium monoperoxyphthalate TBAF tetrabutylammonium fluoride MOM methoxymethyl TBAD =DBAD MoOPH oxodiperoxomolybdenum(pyridine)- TBAI tetrabutylammonium iodide (hexamethylphosphoric triamide) TBAP tetrabutylammonium perruthenate mp melting point TBDMS t-butyldimethylsilyl MPM =PMB TBDPS t-butyldiphenylsilyl Ms mesyl (methanesulfonyl) TBHP t-butyl hydroperoxide MS mass spectrometry; molecular sieves TBS =TBDMS MTBE methyl t-butyl ether TCNE tetracyanoethylene MTM methylthiomethyl TCNQ 7,7,8,8-tetracyanoquinodimethane MVK methyl vinyl ketone TEA triethylamine TEBA triethylbenzylammonium chloride n refractive index TEBAC =TEBA NaHDMS sodium hexamethyldisilazide TEMPO 2,2,6,6-tetramethylpiperidinoxyl Naph naphthyl TES triethylsilyl NBA N-bromoacetamide Tf triflyl (trifluoromethanesulfonyl) nbd norbornadiene (bicyclo[2.2.1]hepta- TFA trifluoroacetic acid 2,5-diene) TFAA trifluoroacetic anhydride NBS N-bromosuccinimide THF tetrahydrofuran NCS N-chlorosuccinimide THP tetrahydropyran; tetrahydropyranyl NIS N-iodosuccinimide Thx thexyl (2,3-dimethyl-2-butyl) NMO N-methylmorpholine N-oxide TIPS triisopropylsilyl N TMANO trimethylamine N-oxide NMP -methyl-2-pyrrolidinone NMR nuclear magnetic resonance TMEDA N,N,N ,N -tetramethylethylenediamine NORPHOS bis(diphenylphosphino)bicyclo[2.2.1]-hept- TMG 1,1,3,3-tetramethylguanidine 5-ene TMS trimethylsilyl Np =Naph Tol p-tolyl TPAP tetrapropylammonium perruthenate TBHP t-butyl hydroperoxide PCC pyridinium chlorochromate TPP tetraphenylporphyrin PDC pyridinium dichromate Tr trityl (triphenylmethyl) Pent n-pentyl Ts tosyl (p-toluenesulfonyl) Ph phenyl TTN thallium(III) nitrate phen 1,10-phenanthroline Phth phthaloyl UHP urea–hydrogen peroxide complex Piv pivaloyl PMB p-methoxybenzyl Z =Cbz Handbook of Reagents for Organic Synthesis Reagents for Heteroarene Functionalization OTHER TITLES IN THIS COLLECTION Catalytic Oxidation Reagents Edited by Philip L. Fuchs ISBN 978 1 119 95327 2 Reagents for Silicon-Mediated Organic Synthesis Edited by Philip L. Fuchs ISBN 978 0 470 71023 4 Sulfur-Containing Reagents Edited by Leo A. Paquette ISBN 978 0 470 74872 5 Reagents for Radical and Radical Ion Chemistry Edited by David Crich ISBN 978 0 470 06536 5 Catalyst Components for Coupling Reactions Edited by Gary A. Molander ISBN 978 0 470 51811 3 Fluorine-Containing Reagents Edited by Leo A. Paquette ISBN 978 0 470 02177 4 Reagents for Direct Functionalization of C–H Bonds Edited by Philip L. Fuchs ISBN 0 470 01022 3 Reagents for Glycoside, Nucleotide, and Peptide Synthesis Edited by David Crich ISBN 0 470 02304 X Reagents for High-Throughput Solid-Phase and Solution-Phase Organic Synthesis Edited by Peter Wipf ISBN 0 470 86298 X Chiral Reagents for Asymmetric Synthesis Edited by Leo A. Paquette ISBN 0 470 85625 4 Activating Agents and Protecting Groups Edited by Anthony J. Pearson and William R. Roush ISBN 0 471 97927 9 Acidic and Basic Reagents Edited by Hans J. Reich and James H. Rigby ISBN 0 471 97925 2 Oxidizing and Reducing Agents Edited by Steven D. Burke and Rick L. Danheiser ISBN 0 471 97926 0 Reagents, Auxiliaries, and Catalysts for C–C Bond Formation Edited by Robert M. Coates and Scott E. Denmark ISBN 0 471 97924 4 e-EROS For access to information on all the reagents covered in the Handbooks of Reagents for Organic Synthesis, and many more, subscribe to e-EROS on the Wiley Online Library website. A database is available with over 200 new entries and updates every year. It is fully searchable by structure, substructure and reaction type and allows sophisticated full text searches. http://onlinelibrary.wiley.com/book/10.1002/047084289X Handbook of Reagents for Organic Synthesis Reagents for Heteroarene Functionalization Edited by André B. Charette Université de Montréal, Montréal, QC, Canada This edition first published 2015 © 2015 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. 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. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold on the understanding that the publisher is not engaged in rendering professional services. 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 Handbook of reagents for organic synthesis : reagents for heteroarene functionalization / edited by André B. Charette, Université de Montréal, Montréal, QC, Canada. pages cm Includes indexes. ISBN 978-1-118-72659-4 (cloth) 1. Organic compounds–Synthesis. 2. Heterocyclic chemistry. 3. Chemical tests and reagents. I. Charette, A. B. (André B.), 1961- editor. II. Title: Reagents for organic synthesis. QD262.H2674 2015 547’.2–dc23 2015020137 A catalogue record for this book is available from the British Library. ISBN 13: 978-1-118-72659-4 Set in 9½/11½ pt Times Roman