Handbook of Reagents for Organic Synthesis Reagents for Heteroarene Synthesis OTHER TITLES IN THIS COLLECTION Reagents for Organocatalysis Edited by Tomislav Rovis ISBN 978 1 119 06100 7 Reagents for Heteroarene Functionalization Edited by Andre´ Charette ISBN 978 1 118 72659 4 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 for 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 online 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. e-EROS is fully searchable by structure, substructure, and reaction type and allows sophisticated full text searches. www.wileyonlinelibrary.com/ref/eros Handbook of Reagents for Organic Synthesis Reagents for Heteroarene Synthesis Edited by Andre´ B. Charette UniversitedeMontr´ eal,´ Montreal,´ Quebec,´ Canada This edition first published 2017 © 2017 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. 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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 is available for this title 9781119952299 (hardback) A catalogue record for this book is available from the British Library. ISBN 13: 978-1-119-95229-9 Set in 9½/11½ pt Times Roman by Thomson Press (India) Ltd., New Delhi. Printed and bound in Singapore by C.O.S Printers Pte Ltd. 10987654321 e-EROS Editorial Board Editor-in-Chief Philip L. Fuchs Purdue University, West Lafayette, IN, USA Executive Editors Andre´ B. Charette UniversitedeMontr´ eal,´ Montreal,´ Quebec,´ Canada Tomislav Rovis Columbia University, New York, NY, USA Jeffrey Bode ETH Zurich,¨ Switzerland Founding Editor Leo A. Paquette The Ohio State University, Columbus, OH, USA Contents Preface ix N,N-Dimethylacetamide Dimethyl Acetal 208 Dimethyl Diazomalonate 215 Introduction xi Dimethyl 2,3-Pentadienedioate 230 Dimethyl 1,2,4,5-Tetrazine-3,6-dicarboxylate 236 Recent Review Articles and Monographs xiii 2,4-Dinitrophenylhydrazine 244 Diphenyl Cyanocarbonimidate 247 Short Note on InChIs and InChIKeys xvii Dirhodium(II) Tetraacetate 249 Acetaldoxime 1 Dirhodium Tetrakis(heptafluorobutyramide) 265 Acetone Hydrazone 7 Di-p-tolylcarbodiimide 267 Acetonitrile 11 Ethyl 2-Diazo-3-oxo-3-phenylpropanoate 273 Acetonitrile N-Oxide 18 Ethyl 2-Diazo-3-oxybutyrate 275 N-Aminophthalimide 19 Ethyl 2-Diazo-4,4,4-trifluoro-3-oxobutanoate 281 1-Amino-pyridinium iodide 24 Ethyl Ethoxymethylenecyanoacetate 284 Ammonium Nitrate 27 Formamidine Acetate 289 Ammonium Acetate 29 Gold(I) Chloride 291 Ammonium Bicarbonate 30 Gold(III) Chloride 298 Benzonitrile N-Oxide 33 Guanidine 322 Benzoyl Isothiocyanate 36 2,5-Hexanedione 327 N-[Bis(methylthio)methylene]-p-toluenesulfonamide 37 Hydrogen Sulfide 330 Bromoacetone 47 Hydroxylamine 335 1-tert-Butyloxycarbonyl-1-methylhydrazine 52 Indium Tribromide 343 2-Chloro-1,3-dimethylimidazolinium chloride 57 Iodine 358 Copper(I) Chloride 61 Iron(III) Bromide 374 Copper(II) Chloride 75 Iron(III) Chloride 379 Copper(I) Iodide 83 Malonyl Chloride 387 Copper(II) Sulfate 93 -Methacrolein N-tert-Butylimine 389 Copper(II) Trifluoromethanesulfonate 104 Methyl glycine 390 Cyclopentadienylbis(triphenylphosphine)cobalt(I) 115 Methyl Isocyanate 393 (Diacetoxyiodo)benzene 119 S-Methylisothiourea 395 Diaminomaleonitrile 128 4-Methyloxazole 397 Diazo(trimethylsilyl)methyllithium 129 Methyl Thioglycolate 398 Dibromoformaldehyde Oxime 135 Oxo(trimanganese) Heptaacetate 401 Dichloro Bis(acetonitrile) Palladium 137 Oxygen 402 Dichlorobis(triphenylphosphine)-palladium(II) 142 Palladium(II) Acetate 415 Di--chlorodichlorobis[(1,2,3,4,5-)-1,2,-3,4,5- Palladium(II) Chloride 449 pentamethyl-2,4-cyclopentadien-1-yl]diiridium 146 Phenyl Isocyanide 467 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone 172 Phenylhydrazine 468 Dichloroformaldehyde Oxime 184 Phenyliodine(III) Bis(trifluoroacetate) 472 Dichlorotris(triphenylphosphine)ruthenium(II) 186 Phosphorus Oxychloride 481 (Diethoxyphosphoryl)acetonitrile oxide 191 Pivalic Acid 489 Diethyl Oxalate 192 Polyphosphoric Acid 497 2,2-Difluoroethylamine 195 Potassium Ethyl Xanthate 503 Diiminosuccinonitrile 199 Potassium Monoperoxysulfate 512 1,3-Diisopropyl-1,3-propanedione 200 Selenium(IV) Oxide 531 2,5-Dimethoxytetrahydrofuran 203 Semicarbazide 542 Silver(I) Hexafluoroantimonate 547 Trifluomethyldiazomethane 607 Sodium Nitrite 550 Trifluoroethylamine 612 Sodium Sulfide 561 Trifluoromethanesulfonic anhydride 616 Sodium Tetrachloroaurate(III) 573 1,1,1-Trifluoro-N-phenylmethanesulfenamide 633 Sulfur 577 2-(Trimethylsilyl)phenyl Triflate 635 N,N,N’,N’-Tetrabromobenzene-1,3-disulfonamide Triphenylphosphinegold(I) Chloride 638 (TBBDS) 583 Tetrakis(triphenylphosphine)-palladium(0) 585 List of Contributors 643 3-Thiapentanedioic acid 594 Thiourea 596 Reagent Formula Index 653 o-Tolyl Isocyanide 598 Subject Index 655 p-Tolylsulfonylmethyl isocyanide 599 Preface The eight-volume Encyclopedia of Reagents for Organic Syn- Reagents for Glycoside, Nucleotide, and Peptide Synthesis thesis (EROS), authored and edited by experts in the field, first Edited by David Crich published in 1995, provided mini-reviews describing the prop- erties and reactions of approximately 3000 reagents. In 2002, Reagents for Direct Functionalization of C–H Bonds the entire EROS collection with updates and additions was Edited by Philip L. Fuchs made available on the Internet under the acronym e-EROS.The second edition of the encyclopedia, EROS-II, was published in Fluorine-Containing Reagents March 2009 containing the entire collection of reagents—4111 Edited by Leo A. Paquette at the time of publication in a 14-volume set. While the com- Catalyst Components for Coupling Reactions prehensive nature of EROS-II and the dynamic expansion of Edited by Gary A. Molander e-EROS render them invaluable as reference works, their very size limits their practicability in a laboratory environment. For Reagents for Radical and Radical Ion Chemistry this reason, a series of sharply targeted and inexpensive one- Edited by David Crich volume Handbooks of Reagents for Organic Synthesis (HROS) was introduced by the original editors of EROS in 1999: Sulfur-Containing Reagents Edited by Leo A. Paquette Reagents, Auxiliaries and Catalysts for C–C Bond Formation Reagents for Silicon-Mediated Organic Synthesis Edited by Robert M. Coates and Scott E. Denmark Edited by Philip L. Fuchs Oxidizing and Reducing Agents Catalytic Oxidation Reagents Edited by Steven D. Burke and Rick L. Danheiser Edited by Philip L. Fuchs Acidic and Basic Reagents Reagents for Heteroarene Functionalization Edited by Hans J. Reich and James H. Rigby EditedbyAndre´ B. Charette Activating Agents and Protecting Groups Reagents for Organocatalysis Edited by Anthony J. Pearson and William R. Roush Edited by Tomislav Rovis This series has continued over the last several years