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Cumulenes in Click Reactions P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come Cumulenes in Click Reactions HENRI ULRICH A John Wiley and Sons, Ltd., Publication iii P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come ii P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come Cumulenes in Click Reactions i P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come ii P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come Cumulenes in Click Reactions HENRI ULRICH A John Wiley and Sons, Ltd., Publication iii P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come This edition first published 2009 C 2009 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. 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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 Ulrich, Henri, 1925– Cumulenes in click reactions / Henri Ulrich. p. cm. Includes bibliographical references and index. ISBN 978-0-470-77932-3 (cloth) 1. Alkenes. 2. Chemical reactions. I. Title. QD305.H7U54 2009 547.412–dc22 2009033775 A catalogue record for this book is available from the British Library. ISBN 978-0-470-77932-3 Set in 10/12pt Times by Aptara Inc., New Delhi, India Printed and bound in Great Britain by CPI Antony Rowe, Chippenham, Wiltshire iv P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come Contents Preface ix Acknowledgements xi 1 General Introduction 1 References 12 2 1-Carbon Cumulenes 13 2.1 Sulfines, R2C S O13 2.1.1 Introduction 13 2.1.2 Dimerization Reactions 14 2.1.3 Cycloaddition Reactions 15 References 23 2.2 Sulfenes, R2C S(O) O25 2.2.1 Introduction 25 2.2.2 Dimerization Reactions 26 2.2.3 Cycloaddition Reactions 26 References 32 2.3 Other 1-Carbon Cumulenes 33 2.3.1 Thiocarbonyl S-Imides 33 2.3.2 Thiocarbonyl S-Sulfides 37 2.3.3 1-Aza-2-azoniaallene Salts 39 References 44 3 2-Carbon Cumulenes 45 3.1 Carbon Oxides, O C O, :C O45 3.1.1 Introduction 45 3.1.2 Cycloaddition Reactions 47 3.1.3 Insertion Reactions 60 References 61 3.2 Carbon Sulfides, S C S, S C O64 3.2.1 Introduction 64 3.2.2 Cycloaddition Reactions 65 3.2.3 Insertion Reactions 75 References 77 3.3 Carbon Nitrides 79 3.3.1 Isocyanates, RN C O79 References 156 v P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come vi Contents 3.3.2 Isothiocyanates, RN C S 168 References 194 3.3.3 Carbodiimides, RN C NR 197 References 232 3.4 Center Carbon Phosphorallenes, P C P 236 3.4.1 Introduction 236 3.4.2 Dimerization Reactions 236 3.4.3 Cycloaddition Reactions 238 References 241 4 1,2-Dicarbon Cumulenes 243 4.1 Ketenes, R2C C O 243 4.1.1 Introduction 243 4.1.2 Dimerization Reactions 244 4.1.3 Trimerization Reactions 252 4.1.4 Cycloaddition Reactions 254 References 312 4.2 Thioketenes, R2C C S 321 4.2.1 Introduction 321 4.2.2 Dimerization Reactions 322 4.2.3 Cycloaddition Reactions 323 References 335 4.3 Ketenimines, R2C C NR 337 4.3.1 Introduction 337 4.3.2 Dimerization Reactions 337 4.3.3 Cycloaddition Reactions 339 References 363 4.4 1-Silaallenes, R2C C Si 366 4.4.1 Introduction 366 4.4.2 Dimerization Reactions 366 4.4.3 Cycloaddition Reactions 367 References 368 4.5 1-Phosphaallenes, R2C C P 368 4.5.1 Introduction 368 4.5.2 Dimerization Reactions 369 4.5.3 Cycloaddition Reactions 370 References 376 4.6 Other Metal Allenes 377 4.6.1 Introduction 377 4.6.2 Cycloaddition Reactions 378 References 389 5 1,3-Dicarbon Cumulenes 391 5.1 Thiocarbonyl S-ylides, R2C S CH2 391 + 5.2 2-Azaallenium Salts, R2C N CR2 394 + 5.3 1-Oxa-3-azoniabutatriene Salts, R2C N C O 395 P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come Contents vii + 5.4 1-Thia-3-azabutatriene Salts, R2C N C S 396 5.5 Phosphorus Ylides 397 References 397 6 1,2,3-Tricarbon Cumulenes 399 6.1 Allenes, R2C C CR2 399 6.1.1 Introduction 399 6.1.2 Dimerization Reactions 402 6.1.3 Oligomerization Reactions 410 6.1.4 Cycloaddition Reactions 412 References 456 6.2 [3] Cumulenes, R2C C C CR2 462 6.2.1 Introduction 462 6.2.2 Dimerization Reactions 462 6.2.3 Trimerization Reactions 464 6.2.4 Cycloaddition Reactions 465 References 468 6.3 [4] Cumulenes, R2C C C C CR2 469 6.3.1 Introduction 469 6.3.2 Dimerization Reactions 469 6.3.3 Cycloaddition Reactions 470 References 470 6.4 [5] Cumulenes, R2C C C C C CR2 470 6.4.1 Introduction 470 6.4.2 Dimerization Reactions 471 6.4.3 Cycloaddition Reactions 472 References 473 7 Noncarbon Cumulenes 475 7.1 Azides, RN N N 475 7.1.1 Introduction 475 7.1.2 Oligomers 476 7.1.3 [3+2] Cycloaddition Reactions 477 References 492 7.1.4 Some Applications in Modifications of Biopolymers 495 Application References 499 7.2 Triazaallenium Salts, RN N+ NR 501 7.2.1 Introduction 501 7.2.2 Cycloaddition Reactions 501 References 502 7.3 Sulfur Oxides 503 7.3.1 Introduction 503 7.3.2 Sulfur Dioxide, O S O 504 7.3.3 Sulfur Trioxide, O SO2 510 References 515 P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come viii Contents 7.4 Sulfur Nitrides 517 7.4.1 N-Sulfinylamines, RN S O and N-Thiosulfinylamines, RN S S 517 7.4.2 Sulfurdiimines, RN S NR 526 7.4.3 N-Sulfonylamines, RN SO2 and Hexavalent Sulfurdiimides 529 7.4.4 Dithionitronium Salts, S N+ N 533 References 536 7.5 Cationic Boron Cumulenes, R2N B NR 538 7.5.1 Introduction 538 7.5.2 Cycloadditions 539 References 540 Index 541 P1: OTE/OTE/SPH P2: OTE FM JWBK368-Ulrich October 5, 2009 9:26 Printer: Yet to come Preface The advent of azide/alkyne ‘click’ chemistry, reintroduced by Sharpless and Meldal earlier this century, has prompted an avalanche of publications in the fields of biochemistry, material science and biopolymers.
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