Jie Jack Li: Name Reactions [PDF]

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Baran Reagents · Bargellini reaction Baran eagents reaction JieReagents Jack ·LiBargellini Cattallani reaction · Danheiser annulation Cattallani C tt ll· Hofmann i reaction rea titionelimination · Danheise DDanheiser h i annulation ann llation ti Elbs oxidation Elb oxidation Elbs o id idation ti McMillan n · Hofmann H f catalyst elimination li i · Anti-Markovnikov ti McMillan catalyst · Anti-Markovnikov Ant Sanford reaction · Yu C-H activation S f d reaction Sanford rea tition · YYu CC-H H activation a ti ation ti Zaitsev elimination Zaitsev Z it elimination Zaitse li i ti

Name Reactions

A Collection of Detailed Mechanisms and Synthetic Applications, Fifth Edition

Name Reactions

Jie Jack Li

Name Reactions A Collection of Detailed Mechanisms and Synthetic Applications Fifth Edition

Jie Jack Li Department of Chemistry College of Arts and Sciences University of San Francisco San Francisco CA, USA

ISBN 978-3-319-03978-7 ISBN 978-3-319-03979-4 (eBook) DOI 10.1007/978-3-319-03979-4 Springer Cham Heidelberg New York Dordrecht London Library of Congress Control Number: 2014930574 © Springer International Publishing Switzerland 2014 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. Exempted from this legal reservation are brief excerpts in connection with reviews or scholarly analysis or material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. Duplication of this publication or parts thereof is permitted only under the provisions of the Copyright Law of the Publisher’s location, in its current version, and permission for use must always be obtained from Springer. Permissions for use may be obtained through RightsLink at the Copyright Clearance Center. Violations are liable to prosecution under the respective Copyright Law. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. While the advice and information in this book are believed to be true and accurate at the date of publication, neither the authors nor the editors nor the publisher can accept any legal responsibility for any errors or omissions that may be made. The publisher makes no warranty, express or implied, with respect to the material contained herein. Printed on acid-free paper Springer is part of Springer Science+Business Media (www.springer.com)

To Prof. Claire Castro

Preface

Four years have gone by since the fourth edition was published and much has happened since then. Professionally, I have moved from industry to academia to teach organic and medicinal chemistry. This change is reflected in my choice to include most of the basic name reactions so that this book will be useful for my undergraduate students. I have also had the opportunity to make corrections to several quinoline- and isoquinoline-related mechanisms. In addition, new name reactions have emerged, and new references appeared for old name reactions. I have added 27 new name reactions to reflect the latest developments in organic chemistry and updated synthetic applications for each old name reaction. By popular demand, a brief biographical description of the inventor of nearly every name reaction has been added to this edition. As in previous editions each reaction is delineated by its detailed step-by-step, electron-pushing mechanism, supplemented with the original and the latest references, especially review articles. Now, with the addition of many synthetic applications, this book is not only an indispensable resource for senior undergraduate and graduate students for learning mechanisms and the synthetic utility of name reactions and preparing for their exams, but it is also a good reference book for all organic chemists in both industry and academia. I wish to thank Dr. Jonathan W. Lockner at Scripps Research Institute and Dr. Jun Cindy Shi of Bristol-Myers Squibb for their help in preparing and proofreading the manuscript. I also wish to thank Prof. Neil K. Garg at UCLA and his students, Grace Chiou, Adam Goetz, Liana Hie, Dr. Travis McMahon, Tejas Shah, Noah Fine Nathel, Joel M. Smith, Amanda Silberstein, and Evan D. Styduhar for proofreading the final version of the manuscript. Their knowledge and input have tremendously enhanced the quality of this book. Any remaining errors are, of course, solely my own responsibility.

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Preface

As always, I welcome your critique! Please send your comments to this email address: [email protected].

October 2013 San Francisco, CA

Jie Jack Li

Table of Contents

Preface ..................................................................................................................... ix Abbreviations ........................................................................................................ xix Alder ene reaction .................................................................................................... 1 Aldol condensation ................................................................................................... 3 Algar–Flynn–Oyamada reaction .............................................................................. 6 Allan–Robinson reaction .......................................................................................... 8 Arndt–Eistert homologation ................................................................................... 10 Baeyer–Villiger oxidation ...................................................................................... 12 Baker–Venkataraman rearrangement ..................................................................... 14 Bamford–Stevens reaction ..................................................................................... 16 Baran reagents ........................................................................................................ 18 Barbier reaction ...................................................................................................... 21 Bargellini reaction .................................................................................................. 23 Bartoli indole synthesis .......................................................................................... 24 Barton radical decarboxylation .............................................................................. 26 Barton–McCombie deoxygenation ........................................................................ 28 Barton nitrite photolysis ......................................................................................... 30 Barton–Zard reaction .............................................................................................. 32 Batcho–Leimgruber indole synthesis ..................................................................... 34 Baylis–Hillman reaction ......................................................................................... 36 Beckmann rearrangement ....................................................................................... 39 Abnormal Beckmann rearrangement ............................................................ 40 Beirut reaction ........................................................................................................ 42 Benzilic acid rearrangement ................................................................................... 44 Benzoin condensation............................................................................................. 46 Bergman cyclization ............................................................................................... 48 Biginelli reaction .................................................................................................... 50 Birch reduction ....................................................................................................... 52 Bischler–Möhlau indole synthesis ......................................................................... 54

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Bischler–Napieralski reaction ................................................................................ 56 Blaise reaction ....................................................................................................... 58 Blum–Ittah aziridine synthesis .............................................................................. 60 Boekelheide reaction .............................................................................................. 62 Boger pyridine synthesis ........................................................................................ 64 Borch reductive amination ..................................................................................... 66 Borsche–Drechsel cyclization ................................................................................ 68 Boulton–Katritzky rearrangement .......................................................................... 70 Bouveault aldehyde synthesis ................................................................................ 72 Bouveault–Blanc reduction .................................................................................... 74 Boyland–Sims oxidation ........................................................................................ 75 Elbs oxidation ................................................................................................ 76 Bradsher reaction.................................................................................................... 77 Brook rearrangement .............................................................................................. 79 Brown hydroboration ............................................................................................. 81 Bucherer carbazole synthesis ................................................................................. 83 Bucherer reaction ................................................................................................... 85 Bucherer–Bergs reaction ........................................................................................ 87 Büchner ring expansion.......................................................................................... 89 Buchwald–Hartwig amination ............................................................................... 91 Burgess reagent ...................................................................................................... 95 Burke boronates...................................................................................................... 97 Cadiot–Chodkiewicz coupling ............................................................................. 100 Cadogan–Sundberg indole synthesis.................................................................... 102 Camps quinoline synthesis ................................................................................... 104 Cannizzaro reaction .............................................................................................. 106 Carroll rearrangement .......................................................................................... 108 Castro–Stephens coupling .................................................................................... 110 CíH activation ..................................................................................................... 112 Catellani reaction......................................................................................... 112 Sanford reaction .......................................................................................... 115 White catalyst .............................................................................................. 117 Yu CíH activation ...................................................................................... 121 Chan alkyne reduction.......................................................................................... 123 Chan–Lam C–X coupling reaction....................................................................... 125 Chapman rearrangement ...................................................................................... 128 Chichibabin pyridine synthesis ............................................................................ 130 Chugaev elimination ............................................................................................ 133 Ciamician–Dennsted rearrangement .................................................................... 135 Claisen condensation ............................................................................................ 136 Claisen isoxazole synthesis .................................................................................. 138 Claisen rearrangements ........................................................................................ 140 para-Claisen rearrangement ........................................................................ 142 Abnormal Claisen rearrangement ............................................................... 144

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Eschenmoser–Claisen amide acetal rearrangement .................................... 146 Ireland–Claisen (silyl ketene acetal) rearrangement ................................... 148 Johnson–Claisen (orthoester) rearrangement .............................................. 150 Clemmensen reduction ......................................................................................... 153 Combes quinoline synthesis ................................................................................. 155 Conrad–Limpach reaction .................................................................................... 157 Cope elimination reaction .................................................................................... 159 Cope rearrangement ............................................................................................. 161 Anionic oxy-Cope rearrangement ............................................................... 163 Oxy-Cope rearrangement ............................................................................ 164 Siloxy-Cope rearrangement ......................................................................... 166 Corey–Bakshi–Shibata (CBS) reagent ................................................................. 168 CoreyChaykovsky reaction ................................................................................ 171 Corey–Fuchs reaction ........................................................................................... 174 Corey–Kim oxidation ........................................................................................... 176 Corey–Nicolaou macrolactonization .................................................................... 178 Corey–Seebach reaction ....................................................................................... 180 Corey–Winter olefin synthesis ............................................................................. 182 Criegee glycol cleavage........................................................................................ 185 Criegee mechanism of ozonolysis ........................................................................ 187 Curtius rearrangement .......................................................................................... 188 Dakin oxidation .................................................................................................... 190 Dakin–West reaction ............................................................................................ 192 Danheiser annulation ............................................................................................ 194 Darzens condensation ........................................................................................... 196 Delépine amine synthesis ..................................................................................... 198 de Mayo reaction .................................................................................................. 200 Demjanov rearrangement ..................................................................................... 202 Tiffeneau–Demjanov rearrangement........................................................... 203 Dess–Martin periodinane oxidation ..................................................................... 206 Dieckmann condensation ..................................................................................... 209 Diels–Alder reaction............................................................................................. 211 Inverse electronic demand Diels–Alder reaction ........................................ 213 Hetero-Diels–Alder reaction ....................................................................... 215 Dienone–phenol rearrangement ........................................................................... 217 Doebner quinoline synthesis ................................................................................ 219 Doebner–von Miller reaction ............................................................................... 221 Dötz reaction ........................................................................................................ 223 Dowd–Beckwith ring expansion .......................................................................... 225 Dudley reagent ..................................................................................................... 227 ErlenmeyerPlöchl azlactone synthesis ............................................................... 229 Eschenmoser’s salt ............................................................................................... 231 Eschenmoser–Tanabe fragmentation ................................................................... 233 Eschweiler–Clarke reductive alkylation of amines .............................................. 235

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Evans aldol reaction ............................................................................................. 237 Favorskii rearrangement....................................................................................... 239 Quasi-Favorskii rearrangement ................................................................... 242 Feist–Bénary furan synthesis ............................................................................... 243 Ferrier carbocyclization........................................................................................ 245 Ferrier glycal allylic rearrangement ..................................................................... 247 Fiesselmann thiophene synthesis ......................................................................... 250 Fischer–Speier esterification ................................................................................ 252 Fischer indole synthesis ....................................................................................... 253 Fischer oxazole synthesis ..................................................................................... 255 Fleming–Kumada oxidation ................................................................................. 257 TamaoKumada oxidation .......................................................................... 259 Friedel–Crafts reaction ......................................................................................... 260 Friedel–Crafts acylation reaction ................................................................ 260 Friedel–Crafts alkylation reaction ............................................................... 262 Friedländer quinoline synthesis............................................................................ 264 Fries rearrangement .............................................................................................. 266 Fukuyama amine synthesis .................................................................................. 268 Fukuyama reduction ............................................................................................. 270 Gabriel synthesis .................................................................................................. 272 Ing–Manske procedure ................................................................................ 273 Gabriel–Colman rearrangement ........................................................................... 275 Gassman indole synthesis .................................................................................... 276 Gattermann–Koch reaction .................................................................................. 278 Gewald aminothiophene synthesis ....................................................................... 279 Glaser coupling .................................................................................................... 282 Eglinton coupling ........................................................................................ 284 Gomberg–Bachmann reaction .............................................................................. 287 Gould–Jacobs reaction ......................................................................................... 289 Grignard reaction.................................................................................................. 291 Grob fragmentation .............................................................................................. 293 Guareschi–Thorpe condensation .......................................................................... 295 Hajos–Wiechert reaction ...................................................................................... 297 Haller–Bauer reaction .......................................................................................... 299 Hantzsch dihydropyridine synthesis .................................................................... 300 Hantzsch pyrrole synthesis ................................................................................... 302 Heck reaction........................................................................................................ 304 Heteroaryl Heck reaction ............................................................................ 307 Hegedus indole synthesis ..................................................................................... 309 Hell–Volhard–Zelinsky reaction .......................................................................... 310 Henry nitroaldol reaction ..................................................................................... 312 Hinsberg synthesis of thiophenes ......................................................................... 314 Hiyama cross-coupling reaction ........................................................................... 316 Hofmann elimination............................................................................................ 318

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Hofmann rearrangement ....................................................................................... 319 Hofmann–Löffler–Freytag reaction ..................................................................... 321 Horner–Wadsworth–Emmons reaction ................................................................ 323 Houben–Hoesch reaction ..................................................................................... 325 Hunsdiecker–Borodin reaction ............................................................................. 327 Jacobsen–Katsuki epoxidation ............................................................................. 329 Japp–Klingemann hydrazone synthesis ............................................................... 331 Jones oxidation ..................................................................................................... 333 Collins oxidation ......................................................................................... 335 PCC oxidation ............................................................................................. 336 PDC oxidation ............................................................................................. 337 Julia–Kocienski olefination .................................................................................. 338 Julia–Lythgoe olefination ..................................................................................... 340 Kahne glycosidation ............................................................................................. 342 Knoevenagel condensation ................................................................................... 344 Knorr pyrazole synthesis ...................................................................................... 347 Koch–Haaf carbonylation..................................................................................... 349 Koenig–Knorr glycosidation ................................................................................ 350 Kostanecki reaction .............................................................................................. 353 Kröhnke pyridine synthesis .................................................................................. 354 Krapcho reaction .................................................................................................. 356 Kumada cross-coupling reaction .......................................................................... 357 Lawesson’s reagent .............................................................................................. 360 Leuckart–Wallach reaction................................................................................... 362 Li A3 reaction ....................................................................................................... 364 Lossen rearrangement........................................................................................... 367 McFadyen–Stevens reduction .............................................................................. 369 McMurry coupling ............................................................................................... 370 MacMillan catalyst ............................................................................................... 372 Mannich reaction .................................................................................................. 374 Markovnikov’s rule .............................................................................................. 376 Anti-Markovnikov ....................................................................................... 377 Martin’s sulfurane dehydrating reagent ............................................................... 379 Masamune–Roush conditions for the Horner–Emmons reaction ........................ 382 Meerwein’s salt .................................................................................................... 384 Meerwein–Ponndorf–Verley reduction ................................................................ 386 Meisenheimer complex ........................................................................................ 388 [1,2]-Meisenheimer rearrangement ...................................................................... 390 [2,3]-Meisenheimer rearrangement ...................................................................... 391 Meyers oxazoline method .................................................................................... 393 Meyer–Schuster rearrangement............................................................................ 395 Michael addition ................................................................................................... 397 Michaelis–Arbuzov phosphonate synthesis ......................................................... 399 Midland reduction ................................................................................................ 401

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Minisci reaction .................................................................................................... 403 Mislow–Evans rearrangement .............................................................................. 405 Mitsunobu reaction ............................................................................................... 407 Miyaura borylation ............................................................................................... 409 Moffatt oxidation.................................................................................................. 411 Morgan–Walls reaction ........................................................................................ 413 Pictet–Hubert reaction ................................................................................. 413 Mori–Ban indole synthesis ................................................................................... 415 Mukaiyama aldol reaction .................................................................................... 417 Mukaiyama Michael addition .............................................................................. 419 Mukaiyama reagent .............................................................................................. 421 MyersSaito cyclization....................................................................................... 423 Nazarov cyclization .............................................................................................. 424 Neber rearrangement ............................................................................................ 426 Nef reaction .......................................................................................................... 428 Negishi cross-coupling reaction ........................................................................... 430 Nenitzescu indole synthesis ................................................................................. 432 NewmanKwart rearrangement ........................................................................... 434 Nicholas reaction .................................................................................................. 436 Nicolaou IBX dehydrogenation ........................................................................... 438 Noyori asymmetric hydrogenation ....................................................................... 440 Nozaki–Hiyama–Kishi reaction ........................................................................... 443 Nysted reagent ...................................................................................................... 445 Oppenauer oxidation ............................................................................................ 447 Overman rearrangement ....................................................................................... 449 Paal thiophene synthesis ...................................................................................... 451 Paal–Knorr furan synthesis .................................................................................. 452 Paal–Knorr pyrrole synthesis ............................................................................... 454 Parham cyclization ............................................................................................... 456 Passerini reaction.................................................................................................. 458 Paternó–Büchi reaction ........................................................................................ 460 Pauson–Khand reaction ........................................................................................ 462 Payne rearrangement ............................................................................................ 464 Pechmann coumarin synthesis ............................................................................. 466 Perkin reaction...................................................................................................... 468 Perkow vinyl phosphate synthesis ....................................................................... 470 Petasis reaction ..................................................................................................... 472 Petasis reagent ...................................................................................................... 474 Peterson olefination .............................................................................................. 476 Pictet–Gams isoquinoline synthesis ..................................................................... 478 Pictet–Spengler tetrahydroisoquinoline synthesis ............................................... 480 Pinacol rearrangement .......................................................................................... 482 Pinner reaction...................................................................................................... 484 Polonovski reaction .............................................................................................. 486

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xvii

Polonovski–Potier reaction................................................................................... 488 Pomeranz–Fritsch reaction ................................................................................... 490 Schlittler–Müller modification .................................................................... 492 Pavorov reaction ................................................................................................... 493 Prévost trans-dihydroxylation .............................................................................. 495 Prins reaction ........................................................................................................ 496 Pschorr cyclization ............................................................................................... 499 Pummerer rearrangement ..................................................................................... 501 Ramberg–Bäcklund reaction ................................................................................ 503 Reformatsky reaction ........................................................................................... 505 Regitz diazo synthesis .......................................................................................... 507 Reimer–Tiemann reaction .................................................................................... 509 Reissert reaction ................................................................................................... 510 Reissert indole synthesis ...................................................................................... 512 Ring-closing metathesis (RCM) ........................................................................... 514 Ritter reaction ....................................................................................................... 517 Robinson annulation ............................................................................................. 519 Robinson–Gabriel synthesis ................................................................................. 521 Robinson–Schöpf reaction ................................................................................... 523 Rosenmund reduction ........................................................................................... 525 Rubottom oxidation .............................................................................................. 527 Rupe rearrangement ............................................................................................. 529 Saegusa oxidation ................................................................................................. 531 Sakurai allylation reaction .................................................................................... 533 Sandmeyer reaction .............................................................................................. 535 Schiemann reaction .............................................................................................. 537 Schmidt rearrangement......................................................................................... 539 Schmidt’s trichloroacetimidate glycosidation ...................................................... 541 Scholl reaction ...................................................................................................... 543 Shapiro reaction .................................................................................................... 544 Sharpless asymmetric amino hydroxylation ........................................................ 546 Sharpless asymmetric dihydroxylation ................................................................ 549 Sharpless asymmetric epoxidation ....................................................................... 552 Sharpless olefin synthesis ..................................................................................... 555 Shi asymmetric epoxidation ................................................................................. 557 Simmons–Smith reaction ..................................................................................... 560 Skraup quinoline synthesis ................................................................................... 562 Smiles rearrangement ........................................................................................... 564 TruceSmile rearrangement ........................................................................ 566 Sommelet reaction ................................................................................................ 568 Sommelet–Hauser rearrangement ........................................................................ 570 Sonogashira reaction ............................................................................................ 572 Staudinger ketene cycloaddition .......................................................................... 574 Staudinger reduction............................................................................................. 576

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Stetter reaction...................................................................................................... 578 Stevens rearrangement ......................................................................................... 580 Still–Gennari phosphonate reaction ..................................................................... 582 Stille coupling ...................................................................................................... 584 Stille–Kelly reaction ............................................................................................. 586 Stobbe condensation ............................................................................................. 587 Stork–Danheiser transposition ............................................................................. 589 Strecker amino acid synthesis .............................................................................. 591 Suzuki–Miyaura coupling .................................................................................... 593 Swern oxidation.................................................................................................... 595 Takai reaction ....................................................................................................... 597 Tebbe reagent ....................................................................................................... 599 TEMPO oxidation ................................................................................................ 601 ThorpeZiegler reaction ....................................................................................... 603 Tsuji–Trost reaction ............................................................................................. 605 Ugi reaction .......................................................................................................... 608 Ullmann coupling ................................................................................................. 611 van Leusen oxazole synthesis .............................................................................. 613 Vilsmeier–Haack reaction .................................................................................... 615 Vinylcyclopropanecyclopentene rearrangement ................................................ 617 von Braun reaction ............................................................................................... 619 Wacker oxidation ................................................................................................. 620 Wagner–Meerwein rearrangement ....................................................................... 622 Weiss–Cook condensation ................................................................................... 624 Wharton reaction .................................................................................................. 626 Williamson ether synthesis .................................................................................. 628 Willgerodt–Kindler reaction ................................................................................ 629 Wittig reaction ...................................................................................................... 632 Schlosser modification of the Wittig reaction............................................. 634 [1,2]-Wittig rearrangement .................................................................................. 636 [2,3]-Wittig rearrangement .................................................................................. 638 Wohl–Ziegler reaction.......................................................................................... 640 Wolff rearrangement ............................................................................................ 642 Wolff–Kishner reduction ..................................................................................... 644 Woodward cis-dihydroxylation ............................................................................ 646 Yamaguchi esterification ..................................................................................... 648 Zaitsev’s elimination rule ..................................................................................... 650 Zhang enyne cycloisomerization ......................................................................... 652 Zimmerman rearrangement .................................................................................. 654 Zincke reaction ..................................................................................................... 656 Zinin benzidine (semidne) rearrangement ........................................................... 659 Index ..................................................................................................................... 661