Organic syntheses based on name reactions a practical guide to 750 transformations a hassner and i namboothiri (auth )

Organic Syntheses Based on Name Reactions Organic Syntheses Based on Name Reactions A Practical Guide to 750 Transformations Third Edition A Hassner, Bar-Ilan University, Israel I Namboothiri, IIT Bombay, India Amsterdam • Boston • Heidelberg • London • New York • Oxford Paris • San Diego • San Francisco • Sydney • Tokyo Elsevier The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands Copyright # 2012, 2002, 1994 Elsevier Ltd 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 without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (ỵ44) (0) 1865 843830; fax (ỵ44) (0) 1865 853333; email: permissions@elsevier.com Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 978-0-08-096630-4 For information on all Elsevier publications visit our website at books.elsevier.com Printed and bound in Great Britain 12 13 14 15 10 Foreword by D Seebach Organic Syntheses Based on Name Reactions When studying chemistry at the Technische Hochschule Karlsruhe, more than 50 years ago, we had to memorize close to 50 Name Reactions for the final examination in organic chemistry The then one and only book on Name Reactions was Krauch-Kunz’s Reaktionen der Organischen Chemie, which tried to be complete at the time In the mean time, synthetic organic methodology has experienced an explosive expansion, which is due to two fundamentally different types of developments: (i) the classical reactions have been modified to become regio-, diastereo-, and enantioselective, and to become catalytic (cf organocatalysis) (ii) The—mostly catalytic—use of transition-metal derivatives has enriched organic synthesis with new types of reactions (cf metathesis), which can almost all be rendered enantioselective by employing chiral ligands on the metal centers Many of the resulting procedures for carrying out certain transformations have turned out to be of broad scope and to be generally reliable, so that—for brevity—they were named after their inventor(s) in synthetic discussions, and that’s all about Name Reactions It is, therefore, not surprising that several monographs on this subject have appeared and that new editions of books on Name Reactions are essential This book first appeared in 1994, a second edition in 2002, and now the third one in 2011, with the number of Name Reactions covered increasing from ca 450 to 550 to over 700, and the number of cited papers from 2100 to 3300 to over 6000 Still, the size of the volume(s) remained “manageable.” Of course, the authors had to make, with a personal bias, decisions about which reactions to include and which to replace (an evolutionary process!) In fact, when browsing through the three editions, one can get the impression that they are quite different books, in spite of the common unique features, which are, first of all, a typical specific experimental procedure and a proposal of a mechanistic course for the covered Name Reaction Then, there are updated references to most recent publications and cross-references to similar transformations with a different name; the quality of the formulae has greatly improved; there are most useful indices of names, reagents, reactions, abbreviations, and group transformations; last but not least, there is a new, larger section entitled “An Overview of Synthesis-Related Name Reaction,” listing, for instance, all Name Reactions, in which aldol-type transformations; cycloadditions; or S, Se, Si, Sn, Bi compounds are involved, to name only three of the 40 entries in this section A scientific book without an excellent index for access to its content is not a good book; this one is, indeed, excellent, not least because of these indices! I went through the pages of this third edition with great pleasure I learned about some transformations, which were new to me To some extent, it was a learning experience like when I studied a textbook as a student The book has, indeed, textbook character and could be used in lab courses as a “cook book” and in advanced organic chemistry courses for problem-solving sessions and as a source of exam questions—without requesting that the students actually memorize the Name Reactions, as in the old days: to cover the fundamental reactivities of organic compounds they must learn names connected with some transformations, reagents, and mechanisms On the other hand, a discussion between top synthetic organic chemists (cf specialists viii Foreword by D Seebach in total synthesis of complex natural products, “synthetic engineers”), with a life-long experience, will inevitably be full of reference to Name Reactions; when the name “pops up,” there is immediate mutual understanding and agreement that there is mention of a generally applicable and reliable chemical transformation In our time of online data bases, such as Chemical Abstract’s Scifinder, Beilstein/Gmelin’s Reaxys (ReactionFlash), Houben-Weyl’s Science of Synthesis, or even Google and Wikipedia (I have successfully tested some of the more “fancy” Name Reactions therein), it is appropriate to ask the question: “Who needs a book on Name Reactions?” The above-mentioned unique features of the third edition of Organic Syntheses Based on Name Reactions will make sure that many organic chemists in academia and in industry will want to have this book on their shelves The success of the second edition and the call for a third edition are evidence for this view Name Reactions are at the core of the art of organic synthesis! Dieter Seebach ETH Zuărich Foreword by S Danishefsky What’s in a Name Reaction?—A Lot To my delight, I discovered that fascinating combination of rigor/hypothesis, hard-core theory/intuition, and commercial-level practicality/artistic elegance known as organic chemistry in a 1954 course at Yeshiva University It was already clear that one of the challenges of Orgo (particularly for the pre-meds) would be the systemization of a huge body of factual data, allowing for retrieval of critical information at critical times (exams, etc.) Our official class textbook was authored by Raymond Brewster at the University of Kansas However, the achievers in the course, whose ranks I sought to enter, also purchased a book written by Louis and Mary Fieser at Harvard Though these two tomes actually covered a very similar body of chemistry, there were some notable differences in style Brewster attempted to rationalize the seemingly unmanageable collection of facts in Orgo under what was then a newly emerging theoretical construct, encompassing mechanisms (still early days for “curved arrows”), effects of structure changes on reactivity, and some of the then very new ideas regarding stereochemistry The Fiesers, in turn, placed heavier emphasis on analogy arguments Fieser mechanisms in those days tended to focus on proposed affinities between substrates and reactants with a high premium on identifying likely leaving groups to be anticipated from various displacements and condensations Much of this line of mechanistic conjecture was captured in a “lasso-type” presentation, wherein stable entities (cf inter alia water, alcohols, amines, halides, etc.) were extruded to drive otherwise mysterious processes forward More so than Brewster, the Fiesers utilized the medium of Name Reactions to facilitate discourse The Name Reaction device in the Fiesers’ treatment tended to focus on overall reaction phenomenology (addition, elimination, aliphatic substitution, aromatic substitution, cycloadditions, condensation, etc.) rather than on intimate goings on below the surface Thus, for instance, the Mannich Reaction would be seen as one which joined a secondary amine a to a carbonyl group (at that time almost always a ketone) through one linking carbon (usually formaldehyde) by extrusion of water With the explosive growth of the number of valuable reactions in organic chemistry and with growing insights into mechanistic issues, the importance of Name Reactions grew The Name Reaction tended to embrace not only a transformation but also a particular mechanistic idea As such, Name Reactions facilitated discussions of both mechanism and synthesis Hence, the role of the Name Reaction classification in facilitating discussion became central Two people, more or less on the same structural and mechanistic pages, could communicate a remarkable amount of information and even prospective ideas through the use of well-chosen Name Reaction descriptors Even today, I find Name Reactions of increasingly great value in organizing my own thoughts about synthesis as well as mechanisms, and in sketching out, if qualitatively, the landscape of our science In principle, it might have been argued that the need for this type of classification is decreasing in the face of powerful searching technology for canvassing large bodies of information, including structures, and even reaction types Surely no one could argue that, in this day and age, the medium of the Name Reaction is the primary way of conveying descriptive and mechanistic information However, the Name Reaction system is still a major aid in x Foreword by S Danishefsky classifying large amounts of information in digestible form As a classroom teacher, mastery of the key Name Reactions is high up on my list of charges to the class on day one of the course Accordingly, I was very pleased to respond to the invitation of Professor Alfred Hassner to comment on his emerging book, which updates, in a most valuable way, an increasing number of Name Reactions Even 57 years after taking the course described above, I remain totally excited at the concept of the awesome power of chemical synthesis The notion that any structure (within reason!), of which the human mind can conceive, is a possible target for chemical synthesis remains to me one of the most noble ideas in the epistemology of science The time is long since past when triumphs in synthesis are viewed primarily as personalized mountain climbing exercises The macho/bravado element is still there, as it is in all artistry-intensive human undertaking but is far less central Synthesis is really about the capacity of the human imagination and human resourcefulness to find ways of joining molecules in a precise, disciplined way with high levels of control Many of these molecules are of immediate interest from a material science or pharmaceutical perspective Others are of interest as probes for evaluating hypotheses in structure theory or in biological signal transduction cascades Aside from its intrinsic appeal to the artistic impulse, synthesis plays an important role in human progress The opportunity of dedicating one’s intellectual imagination to complex problems, many of which are apt to serve the needs of a growingly needful society, must be seen as a great privilege The means for codifying information, which is central in this regard, while rewarding the initiators (even posthumously) of what becomes a Name Reaction retains its special cultural status in assisting the forward march of our science Name Reaction assignments have about them a significant element of intellectual history However (and needless to say), the tracing back of all the antecedents of an idea is actually an endless process What Name Reactions are really about is an agreed upon vocabulary, by convention, for communicating concepts in concise but human terms, befitting one of the most esthetics-intensive of scientific activities, that is, organic synthesis Not surprisingly, with the growing complexity and urgency of problems with which a scientist is faced comes an increasing need for multidisciplinary ventures I would argue (though not without an admittedly strong dose of field chauvinism) that the truly unique gift that chemistry brings to such urgent collaborations is its aspiration for achieving unencumbered synthesis This expansiveness distinguishes chemical synthesis from the unbelievably powerful (more circumscribed) engine of biosynthesis Melding the skill sets of biology-mediated synthesis and unencumbered chemical synthesis is one of the great opportunities at the chemistry/biology frontier While it is well to think about issues of abstract logic and strategy, and ways in which they influence chemical synthesis, the actual drivers of the field are the huge advances in reaction feasibility arising from fundamental studies of methodology and its enabling mechanisms In short, the often unsung heroes of the awesome triumphs in chemical synthesis are the subjects of these Name Reactions (not to speak of their students and postdocs!) I am pleased to congratulate my friend and field colleague, Fred Hassner, and his coauthor Irishi Namboothiri They surely need have no doubt that this latest book on Name Reactions will be read in a continuing way and with great pleasure by their fellow scientists/artists Sam Danishefsky Columbia University Preface to the Third Edition The past 10 years, since the publication of the successful second edition of Organic Syntheses Based on Name Reactions, have witnessed a renaissance in organic synthesis; especially in the discovery of new reagents and chiral catalysts that have spurned development of asymmetric syntheses This has made possible the synthesis of a significant number of complex natural products in an enantioselective manner In the process one continues to notice that many synthetic methods, reagents, and reactions are being referred to in the organic chemistry research community by the names of their discoverers or developers The proliferation of published material in chemical journals has led to journal requirements that authors be more succinct in their publications (witness the fact of extensive Supplemental Material in many journals); hence one often sees procedures or methods referred to by Name rather than by lengthy explanations For the student of organic chemistry, there is the advantage of mnemonic that some prefer One of the comments on the second edition of Organic Syntheses Based on Name Reactions was that we omitted some older and less utilized Name Reactions that had appeared in the first edition Hence for the sake of being comprehensive, we decided to keep such Name Reactions in this revision Further, we have added over 100 new Name Reactions, the choice of which, of course, reflects our own bias, and for that we apologize All reactions have been brought up to date by including recent references where available If possible, we have consulted living authors about their Name Reaction In some cases, no recent references were found, and this may reflect the fact that more modern or simpler reactions are now preferred It appears that people hesitate to refer to reactions by name if they bear more than two or three names This made it desirable to break up reactions such as Hunsdiecker–Borodin–Cristol– Firth–Kochi into the more natural Hunsdiecker (Ag salts of RCOOH), Cristol–Firth (HgO and RCOOH), and Kochi (Pb derivatives) Similarly, in some cases, we separated a Name Reaction from its asymmetric variant, such as the Michael addition or Diels–Alder reaction, in order to avoid them being too cumbersome Even so, since there are now several asymmetric catalysts known for the same reaction, lumping all together would be quite unwieldy Further, we felt it was relevant to finally give credit to major contributions of chemists who developed such well-established reactions as free radical dehalogenation with Bu3SnH (now Kuivila– Beckwith) or carbodiimide coupling reagents (now Sheehan) Ionic liquids and their asymmetric version are also included It will be noticed that quite a few name reactions are related to well known reactions (Friedel–Crafts, aldol, Michael, Grignard) but are known by different names Some reactions are often known by one name but can also be referred to by another name, and this we tried to reflect in the introductory statement by including the other names as well; for instance, Grob Fragmentation also known as Grob–Eschenmoser, or Fokin Cu-catalyzed Click reaction also known as Fokin–Sharpless–Meldal, or Hunsdiecker also known as Hunsdiecker–Borodin There is always a big problem combining the chemistry described by the originator of a Name Reaction with the chemistry developed later and further adjusting it into limited space xii Preface to the Third Edition Obviously, after the original publication, the reaction has sometimes mutated to quite a different animal The Overview section is a new and very important feature to the third edition For instance, the Overview lists syntheses of olefins by CỵC bond formation (over 16 Name Reactions) or by elimination (over 30 Names) This is not only useful for advanced organic chemistry students, but should be very valuable to the researcher as at a glance comparisons of related methods for synthesis of particular functional groups are provided Details can then be found under the names Other Overview sections include asymmetric syntheses, syntheses of amine, cyclopropanes, 5- and 6-membered ring heterocyles and many more Of course this is not meant as a textbook and is limited to named reactions In addition the last few years have seen a proliferation of Pd- (and other metal-) catalyzed coupling reactions; in fact several Nobel prizes were awarded in this field We have therefore also included a brief Overview of Pd catalyzed Name Reactions with a general reaction pathway Wherever possible in the new edition, we have alluded to the mechanism of reactions (probable reaction pathway) by providing an intermediate or a description, yet leaving some freedom for students to supplement details We limited the coverage of reactions since we preferred to keep the size and the cost of the volume manageable The new addition maintains the successful format of providing important references (over 6000); in each case, this includes one of the first references to the reaction and a review reference (marked R) where available Asymmetric syntheses are marked with an * References to books are generally not included Further, a brief example of an experimental procedure is provided in most cases In the experimental, we often refer to “work up” which is usually meant to include, where necessary, washing, drying, extraction, evaporation, and purification (chromatography) Important features of this monograph are the indexes, which should be helpful to the reader: A name index with cross references to multiple names A reagent index An index of abbreviations used A reaction index A functional group transformation index, which allows one to search for conversions of one functional group to another As well as a condensed Overview that includes, among others, aldol type reactions; asymmetric reactions; cyclopropanation; oxidations; rearrangements; S, Se, Si, Sn derivatives, etc The Overview should prove valuable to the synthetic chemist as well as to students in universities, when searching for or comparing procedures In fact this format has led the second edition (even without the Overview) to being adopted as a text in advanced organic chemistry courses We thank our families for their understanding during the extensive work on this book and are grateful to Dr Simcha Meir, Prashant Pavashe, Sundaram Rajkumar, and Mamta Dadwal for their invaluable help in bringing this volume to fruition Mistakes often creep in and we are greatly indebted to Dr Thomas Allmendinger and Mr Simon Allmendinger for checking the manuscript and suggesting corrections that had been overlooked We are very grateful to our editor Dr A Shell for constant encouragement, suggestions as well as proofreading This monograph is dedicated to the memory of Cyd Hassner and of our children Suzie, Douglas and Erica Alfred Hassner Irishi Namboothiri Preface to the Second Edition The success of the first edition of “Organic Syntheses Based on Name Reactions and Unnamed Reactions” and the proliferation of new Name Reactions are the reason for this new revised edition It became obvious that many new reagents and reactions are being referred to in the organic chemistry research community by their names Hence, in addition to over 170 new reactions (previously referred to as Unnamed Reactions) in the first edition, we have included in the second edition 157 new Name Reactions bringing the total to 545 However, we have eliminated the term “Unnamed Reactions” from the title of the monograph, since these reactions are now no longer unnamed Furthermore, we omitted some older and less utilized Name Reactions that appeared in the first edition but have included them in the Name Index, by providing reference to the page number in the first edition (e.g Baudisch 1-27, refers to first edition, p.27) The new additions are all synthetically useful or not immediately obvious transformations In choosing them, emphasis was placed on stereoselective or regioselective reagents or reactions including asymmetric syntheses The latter are particularly timely with the recent Nobel Prize in Chemistry awarded in this area Again we admit our own bias in choosing from the many interesting newer transformations reported in the literature Where possible we have tried to consult with the Name Reaction major author We apologize if inadvertently important reactions were omitted We have maintained the useful format of providing important references (over 3,300); in each case this includes one of the first references to the reaction and a review reference where available Furthermore, an example of an experimental procedure is provided Important features of this monograph remain the indexes, which should be helpful to the reader: A names index with cross references to multiple names; A reagent index; A reaction index, e.g acylations, asymmetric synthesis; epoxidation, heteroannulations, rearrangements, etc.; as well as A functional group transformation index, which allows one to search for conversions of one functional group to another The latter has proved valuable to the synthetic chemist searching for pathways to perform such synthetic procedures Hence, the monograph should be of interest to chemists in industry and academia In fact this format has led to the monograph being adopted as a text in advanced organic chemistry courses We thank our families for their understanding during the travail on this book and are grateful to TEVA Pharmaceutical Co for their support This monograph is dedicated to the memory of my dear wife Cyd (A.H.) Alfred Hassner Carol Stumer Reagents Index Dibutylboryl triflate, 147 3,4-Dichloroaniline, 58 o-Dichlorobenzene, 75 N,N-dichlorocarbamate, 272 2,3-Dichloro-5,6-dicyano-1,4-benzo-quinone (DDQ), 361 2,3-Dichloro-5,6-dicyano-l,4-benzoquinone (DDQ), 361 Dichloromethylene dimethylammonium chloride (Viehe), 503 Dichloromethyl methyl ester (Rieche), 400–401 Dicyclohexylboron triflate, N,N-Dicyclohexylcarbodiimide (DDC), 376, 453 Diethanolamine, 68 Diethyl acetylenedicarboxylate, 40 Diethylaluminum cyanide, 335 Diethylaminosulfur trifluoride (DAST), 445 Diethyl azodicarboxylate (DEAD), 324–325 Diethyl phosphenyl cyanide (CH3CN), 317, 345, 444, 455, 462 Diethyl phosphite, 14, 245, 353, 389 (R,R)-Diethyl tartarate (DET), 247, 436 Diethyl thioacetate, 217 5,10-Dihydrosilanthrene, 36 Diiodo acetate, 95 Diiodosilane (DIS) (Keinan), 255–256 Diisopinocampheylborane (Ipc2BH), 65 Diisopropylamine, 80, 219 Diisopropylethylamine, 1, 147, 356 Dilithium (S)-binaphthoxide, 389 Dimethylacetamide, 74 Dimethyl acetylenedicarboxylate (DMAD), 6, 41, 52 Dimethylamino-2-azaprop-2-ene-1-ylidene dimethylammonium chloride (Gold), 186 Dimethylamino-1-methoxyethene (EschenmoserMeerwein), 143–144 p-Dimethylaminopyridine (DMAP), 48–49, 107, 254, 256, 329, 436–437, 455–456, 533–534 Dimethyl(methylene)ammonium iodide (Eschenmoser), 142 Dimethylformamide, 155 Dimethyl mesoxalate, (4S,5S)-4-(2,2’-Dimethyl-4-phenyl-1,3-dioxan-6-yl)1-phenyl-4H-1,2,4-triazoline-perchlorate, 280 Dimethyl(diazomethyl)phosphonates (Seiferth-Gilbert), 432–433 Dimethyl sulfate, 318 Dimethyl sulfoxide (DMSO), 56, 99, 129, 188, 193, 268–269, 271, 292, 293, 305, 306, 344, 376, 390, 403, 419, 422, 444, 475, 490, 493, 546 1,3-Dimethyl-3,4,5,6-tetrahydro-2(II)-pyrimidone (DMPU), 233, 242 Dimethylthiocarbamoyl chloride, 165, 341 Dimethyl titanium dichloride, 394 3,5-Dinitrochlorobenzene, 197 2,4-Dinitrofluorobenzene, 527 2-(2,4-Dinitrophenyl)-4-acetoxyisoquinolinium chloride, 59 561 2,4-Dinitrophenylhydrazine, 306–307 Dioxirane, 109 Diphenyldisulfide, 151 (S)-2-(Diphenylphosphine)-2’-methoxy-1,1’-binaphthyl (MOP), 209 Diphenylsilane, 273 Dipotassium iron tetracarbonyl, 92–93 2-(Di-t-butylphosphino)biphenyl (Pd:ligand ¼ 2:1), 19 1,3-Dithiane (Corey-Seebach), 429–430 Dodecane, 85 Duolite A-4, 258 E Electrolysis, 266–267 Enediyne, 42, 334 E-Phenyl-tri-n-butylstyrylstannane, 460 4-Ethoxy-3-fluoroaniline, 26 (-)-2-Ethylapopinene, 68 Ethylazido formate, 419 Ethyl bromoacetate, 395, 523 Ethyl chloroformate, 251 Ethylene diammonium acetate (EDDA), 484 Ethyl iodide, 126–127 Ethylmagnesium bromide(chloride), 219 Ethyl orthoformate, 52, 103 F Ferric nitrate, 64 Flash vacuum pyrolysis (FVP), 419 Fluorosulfonic acid, 178–179 Formaldehyde, 77, 142, 144, 198, 303–304, 467, 511–512 Formaldoxime, 55 Formamide, 14, 33–34, 56–57, 61–62, 321–322 Formazan, 26 Formic acid, 144, 158, 262, 287 Fragmentation, 141–142, 192, 382, 433–434, 471, 517 Fremy’s salt, 482 Furoxan, 56 G Grieco reagent, 189t, 324–325, 480 Grignard reagent, 40–41, 52, 61, 65, 70, 96, 151–152, 169, 172, 181–182, 208, 276–277, 370, 407–408, 429, 460, 512–513, 531 Grubbs Catalysts, 194–195, 481 H Heat, 27–28, 77, 102–103, 192, 230, 241, 294, 402, 449 Hexabutyldistannoxane, 332 Hexachlorocyclohexa-2,4 or (2,5)diene-1-one, 196 Hexafluoroacetone, 262 Hexamethyldisiloxane, 318 Hexamethylenetetramine, 122, 447 n-Hexylmagnesium bromide, 172 Hippuric acid, 140–141 562 Reagents Index HMDS, 361, 396 Hydrazine, 22, 173–174, 184, 337, 378, 426, 445, 517, 546 Hydriodic acid, 515 Hydrobromic acid, 49, 63, 240, 249–250, 319, 353, 370, 407, 523 Hydrochloric acid, 15, 41, 43, 169, 301–302, 337t, 379–380, 504 Hydrofluoric acid, 25–26, 166, 314–315 Hydrogen, 105, 298–299, 348, 405, 507–508 Hydrogen hexachloroiridate, 212 Hydrogen peroxide, 38, 320 N-Hydroxybenzene sulfonamide, 10 2-Hydroxybenzyl alcohol, Hydroxy(tosyloxy)iodobenzene, 269, 500–501 Hydroxy(tosyloxy)iodobenzene (Koser), 269 Hydroxylamine, 38, 312, 321, 545 N-Hydroxypyridin-2-thione sodium salt, 34 Hypofluoric acid acetonitrile, 410–411 I Iminopyrimidine, 127 Indol-3-ylidene acetonitrile, 97 Iodine monochloride, 204 p-Iodoanisole, 339 Iodoform, 14 Isobutyraldehyde, B-Isopinocamphenyl-9-borabicyclo[3.3.1]nonanone (Alpine-Borane) (Brown), 318–319 Mercury (lI) trifluoroacetate, 154, 491 Mesitylene, 49 Mesityl oxide, 128 Methanesulfonic acid, 135 p-Methoxybenzoyl peroxide, 83 N-Methoxy-N-methylamide (Weinreb), 512–513 5-Methoxy-2-thienyllithium, 57 Methyl anthranilate, 89 Methyl butynoate, 151 Methyl chloroaluminum amide, 175 Methyl cyanoformate, 300 1-Methylene 2-phenylcyclopropane, 60 g-Methyl-g-decanolactone, 135, 335 Methyl hypofluoride, 410–411 Methyl iodide, 169, 390 Methyllithium (CH3Li), 534–535 Methyl-L-rhamnoside, 17 1-Methyl-4-piperidone, 13 MMPP See Magnesium monoperoxyphthalate (MMPP) Monochloroethylene carbonate, 371 Monoglyme, 83 Montmorillonite K-10, 39, 366–367 Montmorilonite K-10 (Laszlo), 281–282 MoOPH, 502 MOP, 209 Morpholine, 179–180, 546 Morpholinocyclopentene, 41 Mukaiyama catalysts, 330–331 L Lawesson reagent, 283 Lead tetraacetate, 36, 459 Lithium, 68, 93, 183, 264, 378–379 Lithium aluminum hydride (LAH), 67, 76, 100–101, 204, 221, 226, 446, 518 Lithium diisopropylamide (LDA), 6–7, 79, 91, 205, 208, 233, 306, 316, 433–434, 464 Lithium 4,4-di-t-butylbiphenylide (LiDBB), 164 Lithium (lS,2R)-N-methylephedrate, 356 Lithium perchlorate, Lithium tetramethylpiperidine (LTMP), 159, 271, 526 Lithium trimethoxyaluminum hydride, 68, 515 2,6-Lutidine, 256, 286 N Nafion-H (Olah), 166 N-amyl bromide, 52 2-Naphtalenecarboxaldehyde tosylhydrazone, 76 1-(1-Naphthyl)ethyl isocyanate (Pirkle), 381 Nickel chloride, 11–12, 151–152, 219–220, 277–278, 497–498 Nickel cyanide, 399 Nickel peroxide, 267–268 Nitric acid, 314 o-Nitrobenzaldehyde, 19, 184, 284 Nitrogen dioxide, 190–191, 293–294, 327b, 399–400, 449, 472, 495, 524–525 Nitromethane(ethane), 400 o-Nitrophenylselenocyanate, 189 Norepinephrine ester, Nugent catalysts, 194–195, 350 Nugent reagent, 194–195, 350 M Magnesium, 29, 30, 41, 52, 96, 130, 169, 172, 181–182, 185, 190–191, 225–226, 234, 253–254, 317, 327, 349, 370, 429, 439–440, 476 Magnesium amalgam, 138, 285 Manganese dioxide, 317, 480, 529 Martin sulfurane reagent, 304 Meldrum’s acid, 313, 538 Mercuric chloride, 130–131, 138, 341 Mercuric oxide, 108, 275 Mercuric trifluoroacetate, 491 O Organocuprate, 181b, 181–182, 291–292 Osmium tetroxide, 320 Oxalic acid, 511 Oxalyl chloride, 230, 475 Oxazaborolidine (Corey), 125–126 Oxazolidinone, 147, 507 Oxodiperoxymolybdenum(pyridine) hexamethylphosphoric triamide (MoOPH) (Vedej), 502 Ozone, 203, 472, 546 K KAPA, 214 Reagents Index P Palladium, 209, 210, 449, 460–461, 473–474, 534 Palladium acetate, 19 Palladium/BaSO4 (Pd/BaSO4), 291, 406 Palladium/Carbon (Pd/C), 30, 40, 46–47, 171, 197, 337, 406, 484, 541 Palladium chloride, 73, 449, 450, 507, 520, 523 Palladium diacetate, 210 Palladium hydroxide, 367–368 Palladium tetrakistriphenylphosphine, 8, 219–220, 277–278, 338–339, 439–440, 449, 473–474, 494 PdCl(Z3-C3H5)2, 209 PEG-Burgess reagent, 74 Pentacarbonyl[methoxy(phenyl)carbene], 156 Peracetic acid, 312 Perchloric acid, 17–18, 21, 24, 149, 429–430, 507, 545 (Perfluoroalkyl)trimethylsilane (Ruppert), 412–413 Periodinane, 123 Petasis Ti catalysts, 371–372, 481 Phase transfer catalyst (PTC), 49, 155–156, 265, 269–270, 450t, 450 Phenyl isocyanate, 223 Phenylmagnesium bromide, 253 4-Phenylpyridine-N-oxide (4-PPNO), 235 Phenylselenyl bromide, 91 2-(Phenylsulfonyl)-3-phenyloxaziridine (Davis), 119 Phosgene, 354 Phosphazene base (Schwesinger base), 427 Phosphite, 2, 11–12, 14, 51, 245, 323–324, 388–389, 453 Phosphite triethyl, 245, 371, 502 Phosphonium salt, 7–8, 519, 520, 524–525 Phosphorous pentachloride, 39, 63, 440–441, 448–449, 509 Phosphorous pentasulfide, 504 Phosphorous pentoxide, 4, 30, 39, 48, 106, 135, 230, 312, 335, 376–377, 442, 475, 504 Photochemical reaction, 108 Phthalocyanine ligand (V, Mn, Oo, Ni, Pd), 135–136 Platinum black, 98 Platinum oxide, 213, 398 Polyphosphoric acid (PPA), 46–47, 294 Potassium acetoacetate, 236 Potassium-3-aminopropylamine (KAPA), 63–64, 214–215 Potassium carbonate, 174, 212 Potassium cyanide, 6–7, 70, 120, 178, 235–236, 258, 279–280, 397–398, 399–400, 464, 536 Potassium hydroxide (KOH), 6–8, 15, 26, 47, 50, 58, 77, 84–85, 92–93, 111, 139–140, 167, 173–174, 195, 197, 222, 236, 237–238, 245b, 245–246, 265, 272, 287–288, 321, 328–329, 333, 336, 337, 361, 369, 370, 375–376, 385–386, 391, 392, 400, 406, 414, 426–427, 438, 440, 486–487, 493, 511, 523–524, 526, 529, 536 Potassium nitrosodisulfonate (Fremy’s Salt), 482 Potassium permanganate (KMnO4), 84, 227, 480, 530 Potassium peroxydisulfate, 137 Potassium persulfate, 58, 137, 170 563 Pressure, 5, 168, 170, 255, 303, 347, 365, 398, 405, 406, 542 Proline, 28, 125–126, 152–153, 199, 292–293, 403, 538 1,3-propanedithiol, 430 Propargyl esters, 488–489 Pyridine, 17b, 17, 26, 27–28, 32, 35, 49, 53–54, 84, 100, 105–106, 138, 185, 189, 197, 200, 230, 251, 254, 261, 274, 280–281, 418 Pyridine p-toluenesulfonate (PPTS), 189–190 Pyridinethiol, 102–103 Pyridinium chlorochromate (PCC) (Corey), 100, 480 Q Quinidine, 435–436 Quinone, 132, 227, 303–304, 339, 409, 415, 482b, 483 R Rhenium heptoxide, 256 Rhodium chloride dicyclooctadiene, 246–247, 349 Rhodium diacetate, 71–72 Rhodium dichlorodicarbonyl, 514 Rhodium tetracarbonyl (Alper), 8–9 Rhodium tris triphenylphosphine carbonyl, 8–9 Ruthenium (IV) oxide, 128, 288–289 Ruthenium trichloride, 140–141, 359, 510–511 S Salen, 235 Samarium, 242, 248 Samarium iodide, 94–95 Scandium triflate, 444 Schrock catalyst, 194 Schrock catalysts, 194–195 Schwartz cyclopentadienyl zirconium, 425 Schwesinger base, 241, 505 Selenium dioxide, 195, 401 Silver acetate, 385–386 Silver benzoate, 12 Silver oxide, 390 Silver salts, 121 Silver tosylate, 269 Silver triflate, 121 SMEAH (Red Al), 100–101 Sodium acetate trihydrate, 186 Sodium amalgam, 163–164 Sodium amide, 84, 199–200 Sodium azide, 155 Sodium bis-(2-methoxyethoxy) aluminium hydride (Red Al), 100–101 Sodium borohydride, 8–9, 69, 82–83, 130–131, 135–136, 145–146, 159, 181, 237, 253, 258, 287, 295, 316, 388, 472–473, 486–487, 540–541 Sodium cyanide, 498 Sodium cyanoborohydride, 510 Sodium dithionite, 268, 304 Sodium hydride, 27–28, 36–37, 85, 99, 124, 131, 132, 143, 150, 228–229, 269–270, 306, 336, 373, 383, 425–426, 444, 462–463, 524–525 Sodium hydrogen oxalate, 258 Sodium hypochlorite, 380, 438 564 Reagents Index Sodium nitrite, 26, 123, 400 Sodium periodate, 4–5, 17, 91, 128, 204, 286, 359, 429–430 Sodium persulfate, 303–304 Sodium potassium tartrate, 145 Sodium triacetoxyborohydride, 55 Sparteine, 107–108, 228 Stetter catalysts, 409–410 Suberic acid, 50 Sulfer trioxide, 129 Sulfinimine, 119 N-Sulfonylhydroxylamine, 10 2-Sulfonyl oxaziridine (Davis), 119 Sulfur, 13, 153, 179–180, 214, 272, 434–435, 487, 522 Sulfur (Sulfuran) (Martin), 304 Sulfurane, 304 Sulfur dichloride, 272 Sulfuric acid, 20, 122, 160, 208, 262–263 T Tebbe catalysts, 481 Tebbe Ti-Al reagent, 481 2,4,5,6-Tetraaminopyrimidine, 50 Tetrabutyl ammonium azide, 204 Tetrabutylammonium difluorotriphenyl stannate (Gingras), 183–184 Tetrabutylammonium fluoride (TBAF), 219 Tetradecyltrimethylammonium bromide, 49 Tetraethylammonium iodide, 497 Tetrafluoroboric acid, 32, 305, 358, 417, 420, 507 Tetrakis(triphenylphosphine)palladium(O), 460, 461 Tetrakis(diethylamino)titanium (Reetz), 394 Tetramethyl ethylenediamine (TMEDA), 66, 205, 433–434, 445–446, 477 Tetramethylpiperidide lithium (LTMP), 159, 270–271, 525–526 Tetramethylsilane, 363 Tetramethyl-t-butylguanidine, 33 Tetraphenylporphyrin (Schenk), 418 Tetrapropylammonium perruthenate (Ley-Griffith), 288–289 1,2,4,5-Tetrazine (Boger-Carboni-Lindsey), 53–54 Thalium tris(trifluoroacetate) (Larock), 280–281 Thiazoline (Rhodanine), 13, 173 Thiobutyric acid, 143 b-Thio-butyrolactone, 94 Thionyl chloride, 73–74, 455 Thiophenol, 154, 165b, 287b, 341b Thiourea dioxide, 322 2-Thioxo-4-thiazolidone, 188 Tin chloride (II/IV), 167, 337, 448–449, 456 Tin hydroxide, 190 Titanium alkoxide, 436 Titanium complex (3THF Mg2Cl2 TiNCO) (Shibasaki), 327, 439 Titanium tetrachloride, 6–7, 49, 88, 96, 107–108, 112, 225–226, 253, 327, 356, 399, 400–401, 415–416, 439–440, 477, 478, 538 TMEDA, 66, 205, 433–434, 445–446, 477 p-Toluenesulfonic acid, 16, 326, 420 p-Toluenesulfonyl azide, 366 p-Toluenesulfonyl chloride, 336 p-Toluenesulfonyl methylisocyanate (TosMIC) (Van Leusen), 499–500 TosMIC, 499–500 N-Tosylaziridinylcyclohexanol, 366 Tosylhydrazone, 27b, 75–76, 433–434 Trans-1,2-cyclohexanediol, 11 trans-Di(m-acetato)bis[di-o-tolyl phosphino) benzyl] dipalladium(II) (Palladacycle)-(Heck-Fujiwara), 213, 473–474 Triacetoxyborohydride, 55, 162 1,2,4-Triazine, 47, 54 Tributylstannane, 36–37, 82–83, 181, 249, 275–276, 465–466 Tributyltin chloride, 319–320 2,4,6-Trichlorobenzoyl chloride, 533–534 Triethylaluminum, 7–8, 36, 48, 171, 177, 268, 284–285, 449, 464–465, 505, 523, 533 Triethylamine, 1, 19, 22, 210, 334, 353, 384 Triethylbenzylammonium chloride, 265 Triethyloxonium tetrafluoroborate (Meerwein), 309 Triethylsilane, 62 Triethylsilylhydrotrioxide, 384 Trifluoroacetic acid/anhydride, 254 (Trifluoromethyl)trimethylsilane (Ruppert), 412 Trimethylsilyl chloride, 223–224 Trimethylsilyl cyanide, 464 Trimethylsilyl diazomethane, 93 Trimethylsilyl iodide, 243, 540 Trimethylsilyl thiazole (Dondoni), 130–131 Trimethylsulfoxonium ylide, 419 Tri-n-butyl stannane, 33 Triphenylbismuth diacetate, 116 Triphenylcarbinol, 20 Triphenylphosphine, 51, 497 Triphenylphosphine copperhydride (Stryker), 470 2,4,6-Triphenylpyrylium tetrafluoroborate, 252 1,1,1-Tris(acetyloxy)-1,1-dihydro-1,2-benzo-iodoxol-3 (1H)-one (Periodinane) (Dess- Martin), 123 Tris(3,6-dioxaheptyl)amine, 450 Tris(triphenylphosphine)chlororhodium (Wilkinson), 521 Tris(trimethylsilyloxy)ethylene (Wissner), 524 U Ultrasound, 63–64, 395, 484 Urea, 45, 111, 294, 305, 329, 436–437 Urea-hydrogen peroxide (UHP), 239 V Vanadium oxytrifluoride (Liepa), 290 Viehe imminium reagent, 503 Vinyl chloroformate, 354 W Wilkinson, 521 X Xanthates, 287–288 Reagents Index Y Ytterbium, 170–171 Ytterbium triflate (Mukaiyama), 331 Z Zinc, 29, 90, 152–153, 165, 171, 214, 260, 355–356, 395, 395 565 Zinc amalgam, 90 Zinc chloride, 6–7, 43, 49, 54, 113, 128–129, 163–164, 166, 167, 198, 225, 229–230, 305–306, 338–339, 522–523, 535 Zinc copper couple, 260, 307 Zinc cyanide, 178–179 Zirconocene (methyl) chloride, 72 Reactions Index Page numbers followed by t refers to top, b refers to bottom A Amino acid labeling, 417 Acetoxylation, 483 Acetylene coupling, 185, 449, 457t Acetylene synthesis, 168, 352 Acetylene zipper reaction, 63b Acridine synthesis, 43t, 496t, 498b Acyl anion, 130–131, 279–280, 409–410, 429–430, 431, 467 Acylation, 7–8, 24, 59–60, 115, 166, 229–230, 273, 313, 356, 431, 464–465, 493 Acyloin condensation, 384–385 Addition, 170–171, 181–182, 234, 457b Addition regioselective, 204, 302–303 Alcohol dehydration, 73–74, 324–325 Alcohol deoxygenation, 36–37 Alcohol oxidation, 79–80, 100, 102, 123, 129, 239, 376, 418, 475 Aldehyde oxidation, 121, 380, 485–486 Aldolization, 330–331 Aldolization enantioselective, 147, 199t, 228 Aldol of vinylepoxides, 282 Aldose degradation, 411, 527 Alkene acylation, 273 Alkylation, 87 Alkylation, acylation, 166 Alkylation geminal, 363 Alkylation mono, 162 Alkyne synthesis, 93t, 101 Allene synthesis, 105t, 130t Allylation, 65, 220, 255t, 296, 346b, 371–372, 374, 415b, 446–447, 494, 534 Allylation enantioselective, 65, 446, 534 Allylation stereoselective, 220 Allyl-Enol coupling, 488t Allylic acetamidation, 143b Allylic oxidation, 100, 195, 257t, 419, 491, 495 Amidation, 76, 321b, 402, 471 Amidine synthesis, 120, 175 Amination, 55, 73, 84, 272, 287, 293–294, 323, 434–435, 438–439, 493 Amine displacement, 252 Amine methylation, 144 Amine oxidation, 119, 251b Amine synthesis, 122, 162, 173–174, 359, 371–372 Amino acid synthesis, 40, 57, 114t, 139–140, 213, 351, 422b, 469, 508, 522b Aminoacrylate synthesis, 218b Aminoalkylation, 70t 2-Aminoheterocycles synthesis, 179 Aminoimidazole synthesis, 192b Aminomethylating agent, 186t Aminomethylation, 301–302 Aminophosphonate synthesis, 245t a-Aminophosphonic acid synthesis, 353b Amino sugar synthesis, 17t Ammonium ylide rearrangement, 448t Annulation, 42, 112, 169, 176b, 207, 280–281, 361–362, 365, 403t, 513t Annulation regiocontrolled, 112 Antracene synthesis, 159 Aromatic aldehyde synthesis, 55b Aromatic arsonylation, 37 Aromatic carboxylation, 399b Aromatic cyanation, 407t Aromatic fluorination, 420t Aromatic tritylation, 20 Aromatization, 40, 176–177, 430 Arsonilation, 38b Arsonylation, 37, 406t Arylation, 32b, 116, 170t, 186b, 378b, 388t Arylation carboxylation, 170t Aryl cyanide synthesis, 321t Aryl halide amination, 73t Arylpyridine synthesis, 83 Asymmetric aldol reaction, 1, 117, 292b Asymmetric allyl alcohol synthesis, 355b Asymmetric hydrogenation, 246, 293–294 Asymmetric Mannich reaction, 292t Asymmetric Michael reaction, 343 Asymmetric olefin hydration, 209 Asymmetric phosphonylation, Asymmetric S-oxidation, 247 Asymmetric Stetter reaction via carbenes, 409 Asymmetric synthesis, 114–115, 117, 176, 209, 220, 293–294, 305–306, 316, 336, 355–356, 408, 415–416, 422–423, 463, 469, 498, 522–523, 546 Aza-bicycle synthesis, 516t Azaheterocycle synthesis, 440b Azaheterocyclization, 440b Azide synthesis, 155 Aziridine isomerization, 173t Aziridine or triazoline synthesis, 418b Aziridine synthesis, 51, 204, 221t, 513b Azoxybenzene rearrangement, 509t 568 Reactions Index B Benzidine (Semidine) rearrangement, 543 Benzotriazine synthesis, 26, 46b Benzoxazine synthesis, 268t Benzylic acid rearrangement, 290 Bromination, 147, 196, 211t, 250, 319, 364, 528t Bromoalkene reduction, 353t C Calixarene synthesis, 544 Carbanion rearrangement, 193 Carbohydrate rearrangement, 153b Carbonyl a-functionalization, 206t Carbonylation, 8, 92b, 178b, 405b, 521 Carbonyl coupling, 307 Carbonyl olefination, 253t Carbonyl synthesis, 460b Carboxylation, 170t, 262b, 267, 399b, 476 Carboxymethylation, 530t Cascade reaction, 484t Catalytic nitrogenation, 327t C-C coupling reaction, 29 C-C coupling via silanes, 219 Ce ether oxidation, 489 Chiral cyclohexenone synthesis, 154 Chiral cyclopentane synthesis from sugars, 501 Chiral induction, 5, 305b Chiral synthesis, 501 Chloroalkylation, 49 Chloromethylation, 49 Chromanone synthesis, 245b Cinnoline synthesis, 337t, 400t Cleavage, 27t, 30, 39, 40, 128, 131, 138–139, 164, 189–190, 199b, 237, 243, 274, 286, 314–315, 347, 348, 384, 437, 440b, 495, 521, 540t, 546 C¼O Homologation, 130b 3-Component amine synthesis, 371b 3-Component condensation, 538 Condensation, 17, 50, 88t, 245–246, 261t, 279b, 330–331, 363b, 384b, 392, 440, 462b, 485, 495, 505–506 Conjugated aldehyde synthesis, 40b Conversion, 337–338, 415 Coumarin rearrangement, 370 Coupling, 183–184, 210, 260, 263t, 307, 369t, 473, 488t, 533t Crisscross cycloaddition, 22 Criss-cross reaction, 22 Cross coupling, 210, 263t, 307, 338, 461 Crown ether, 279–280, 360, 368, 374 Cr oxidizing reagents, 100t Cryptands, 284b Cryptand synthesis, 284b Cumulene ylides, 44 Cu-Zn C-C coupling, 260 Cyanation, 407t, 499–500 Cyanohydrin alkylation, 464t Cyano succinic acid synthesis, 162b cyclization, 23, 30, 32, 42, 50, 59b, 72, 75t, 82b, 95, 151b, 182, 199t, 248, 249b, 256, 261–262, 275–276, 298, 348, 357, 362, 404, 440b, 465, 466, 488–489, 498, 507, 509, 539–540 Cyclization chiral, 154 Cyclization dipolar (2ỵ2; 1ỵ3; 4ỵ2), 4445, 121t, 364b, 367, 432–433 Cyclization enantioselective, 199t Cyclization oxidative, 256, 507 Cyclization photochemical, 121 Cyclization regioselective, 131132 Cyclization stereoselective, 151b Cyclization thermal (4ỵ2), 53t Cycloaddition (2ỵ2; 3ỵ1; 4ỵ2; 5ỵ2; 6ỵ2), 6t, 22, 4445, 124–125, 364b, 367t, 454 Cycloaromatization, 42, 334 Cyclobutanone synthesis, 180 Cyclobutenone rearrangement, 325 Cyclocondensation, 88t, 440–441, 457t Cyclohexadiene synthesis, Cyclohexene synthesis, 124b Cyclohexenone synthesis, 154, 169, 198 Cyclopentenone annulation, 365 Cyclopentenone synthesis, 335b, 357t, 365 Cyclopropanation, 86b, 156–157, 176, 329, 374, 432–433, 441, 488–489, 495 Cyclopropane synthesis, 165t, 375t Cyclopropyl ketone rearrangement, 92t D De-alkoxycarbonylation, 271 Dealkylation, 301t, 354 Deamination, 33, 122b, 190t, 275–276 Decarbonylation, 521 Decarboxylation, 34, 57, 79, 111–112, 198, 200, 263–264, 266–267, 392, 411, 471, 492 Degradation, 30t, 63t, 109–110, 223t, 319t, 411, 438, 451, 511t, 527 Dehydration, 10b, 48, 73b, 304, 324–325, 430–431 Dehydrohalogenation, 306 Diarylmethane synthesis, 18 Diaziridine synthesis, 421 Diazirine synthesis, 421 Diazo-olefin cycloaddition, 367t Diazo reaction, 161, 396t, 432b Diene synthesis, 518t Diene synthesis, regio and stereo controlled, 113 Dienone-phenol rearrangement, 16 Dihalocarbene, 340, 432t Dihydropyridine synthesis, 201b Dihydroxylation asymmetric, 435 Dimerization, 225b, 253b, 266–267, 497 Dinitrile cyclization, 249b Diol elimination, 174b Directed hydrogenation catalyst, 105b Direct esterification, 455b Dismutation, 485b Reactions Index Displacement, 10b, 153–154, 155b, 183–184, 189, 252, 255–256, 268–269, 324, 328–329, 505t, 531, 534b Displacement with chirality transfer, 534b Domino reaction, 484t E Electrochemistry, 266–267, 466 Electrolysis, 266b Elimination, 30, 36–37, 73–74, 75b, 85, 91, 94–95, 97–98, 101, 142, 154–155, 165, 168–169, 174–175, 189, 192, 201, 203–204, 222, 237b, 242, 253, 268–269, 302–303, 304, 319–320, 382, 391, 415, 507, 540–541 Enamine homologation, 41 Enantioselective allylation, 133, 273 Enantioselective borane reducing agent, 98 Enantioselective Michael addition, 152 Ene reaction, 5, 95–96, 151–152, 195, 419–420 Enol ether homologation, 340 Enol ether synthesis, 54 Enone synthesis, 415t Epoxidation, 99, 109t, 235t, 239b, 344, 386, 410–411, 436t Epoxidation asymmetric, 109, 235t, 239–240, 386, 436t Epoxide homolysis, 350 Epoxide rearrangement, 311t Epoxide synthesis, 114b Ester condensation, 88t, 384–385 Ester homologation, 270 Esterification, 324–325, 331–332, 368, 436–437, 455b, 533–534 Ester reduction, 308b Ester synthesis, 198, 392b Ether cleavage, 243 Ether dealkylation, 301t Etherification, 27–28 F Fe catalyzed C-C Coupling, 172 Flavone synthesis, 15, 23 Fluorination, 420t, 445t Fluoroalkane synthesis, 474 Fluoroalkylation, 262t Formylation, 396b, 400b, 460t, 503 Fragmentation, 39, 141–142, 192t, 382, 433–434, 471, 517 Free radical C-C coupling, 181t Free radical reaction, 255 Free radical substitution, 323t Functional Group via hydroboration, 66 Functionalization, 35, 471, 500–501 Functionalization asymmetric, 209 Furan annulation, 176b Furan synthesis, 150 G Glucosamine rearrangement, Glycine equivalent, 269b 569 Glycol oxidation, 106 Glycosidation, 249t, 265, 346t Guanine synthesis, 537 H Halide displacement, 155b, 268–269, 531 Haloalkylation, 49 Haloaniline rearrangement, 357b Halodecarboxylation, 108, 232 Halogenation, 232, 391 Halogenation regioselective, 196 Halogen azide and aziridine synthesis, 204 Heteroannulation, 280–281 Heterocyclization, 72, 510b Higher order cyanocuprates, 291b Homologation, 12, 34, 41, 71b, 130b, 188, 189, 258, 270, 340 Homologative epoxidation, 99 Homologous Diels-Alder reaction, 514 Homolysis, 350 Hydantoin synthesis, 70b Hydration, 209, 274b Hydrazino acid synthesis, 438t Hydrazone synthesis, 236 Hydroamination, 216–217, 488–489 Hydroboration, 65, 66, 67, 246–247, 355–356, 446 Hydrogenation “adjustable,”, 135–136 Hydrogenation asymmetric, 246, 293–294 Hydrogenation ionic, 278 Hydrogenation stereoselective, 349 Hydrogenolysis, 367b Hydrolysis, 70, 130, 159, 230, 324, 412, 422, 464 Hydromagnesation, 96 Hydroperoxide rearrangement, 107t Hydroquinone monoether formation, 413 Hydroquinone synthesis, 131 Hydroxamic acid synthesis, 10t Hydroxycyclopropanation, 276 5-Hydroxyindole synthesis, 339 Hydroxylation, 119, 206, 320, 480t, 502, 505 Hydroxylation stereospecific, 480t Hydroxymethylation, 387 Hydrozirconation, 425t I Imidazole cleavage, 27t Imidazole synthesis, 61b, 509b Imino ether synthesis, 379 Indole synthesis, 47, 157, 285, 298t, 339, 378t Indolizine synthesis, 84b Indoxyl synthesis, 19t Iodination, 32t, 101, 255–256 Iodination reagent, 32t Ionic hydrogenation, 278 Iridium hydride reduction, 211b Isatin synthesis, 416 Isomerization, 222, 412 570 Reactions Index Isoquinoline synthesis, 48t, 280–281, 377 Isoquinolinium cycloaddition, 59t Isothiocyanate synthesis, 251t K Ketone oxidation, 21 Ketone perfluoroalkylation, 412b Ketone synthesis, 67, 111b, 183t, 203b, 512 Ketone transposition, 540b L Lactam macrocyclization, 50, 102–103, 510t b-Lactam synthesis, 182, 259t Lactonization, 331, 533b Lanthanide (Yb) reaction, 170b Lithiation, 206b, 362, 445–446 M Macrocycle synthesis, 50b Macrocyclic lactum synthesis, 510t Macrolactonization, 102b, 331–332, 436–437, 455–456, 495 Mercuric catalyzed hydration, 274b Metal-free bond activation, 43b Metathesis, 194, 477 Methoxycarbonylation, 300 Methylenation, 142, 481 Michael initiated ring closure (MIRC), 205 Migration (Alkyl), 126–127 MIRC ring clousure, 205 Monophenylation of diols, 116b Multicomponent aminoacid synthesis, 40t Multi component reaction, 70, 192–193 Multi step reaction, 484, 496 N N-Acyllactam rearrangement, 333t N-Acyl rearrangement, 254 N-Heterocycles by reverse demand Diels-Alder, 53b N-Hetorocycle amination, 84t Nitration, 196, 281–282, 314t, 472t, 540–541 Nitration regioselective, 196 Nitrite photolysis, 35t Nitroaldol condensation, 212 Nitrogenation catalytic, 327t Nitrosation, 57, 490 Nitrosophenol synthesis, 38t N-Oxide Rearrangement, 312, 382 Nucleoside synthesis, 216t, 505b O O-Hydroxyaniline synthesis, 58 Olefination, 27–28, 35b, 91, 93, 103, 141, 189t, 228b, 241, 242, 250, 253t, 373, 433, 477, 480b, 481 Olefination of diols, 103 Olefination stereoselective, 253 Olefination via aziridinylhydrazones, 141 Olefination via selenides, 91 Olefin carbonylation, 405b Olefin dihydroxylation, 320 Olefin metathesis, 194 Olefin or diol cleavage, 286 One-pot alcohol olefination, 480b Organometallics, 338–339 Ortho lithiation, 206b, 445b (Oxa) di-p-methane rearrangement, 542 Oxazole rearrangement, 104 Oxazole synthesis, 116t, 158t, 235b Oxazoline asymmetric synthesis, 316 Oxazolone synthesis, 140 Oxidation, 4b, 21, 58, 100t, 106, 119, 123, 128t, 137t, 227, 239, 251b, 257t, 267–268, 288, 344, 355t, 401, 419, 451, 475, 482, 489, 491t, 507t Oxidation aymmetric, 247 Oxidation-reduction, 77 Oxidation selective, 344 Oxidative aryl rearrangement, 250 Oxidative cyclization, 256, 507 Oxindole synthesis, 19b, 177, 218t Ozonide formation, 203t P Penicillin rearrangement, 326 Peptide coupling, 533t Peptide synthesis, 226, 314b, 331–332, 436–437, 495, 530b, 533 Perfluoroalkylation, 412b Phase transfer catalyses, 49, 155–156, 265, 351, 450t, 523–524 Phenanthrene synthesis, 30, 290b Phenanthridine synthesis, 376b Phenol alkynylation, 237b Phenol ester rearrangement, 167b Phenol oxidation, 4b, 111t Phenylation, 32–33, 116 Phosphazene base, 427 Phosphole synthesis, 308t Phosphonate synthesis, 11 Phosphonation, 308, 318t, 371t Phosphonation stereoselective, Phosphonium rearrangement, Phosphonylation, 2, 318t Phosphonyl chloride synthesis, 89 Phosphoramidate synthesis, 14 Photochemical iodo functionalization, 471 Photocoupling, 86, 121, 364b Photocycloaddition, 121t Photolysis, 27b, 35t, 224, 232 Phthalimide rearrangement, 174t Polymers and peptide synthesis, 314b Polynuclear aromatics, 137b, 422 Porphyrin synthesis, 297 Pteridines synthesis, 50t Purine synthesis, 490b Pyrazine synthesis, 178t Pyridine benzylation, 279t Pyridine synthesis, 17b Pyridone synthesis, 345 Pyrimidone synthesis, 45 Pyrrole synthesis, 88b, 361t, 378, 423, 539b Reactions Index Pyrrolidine synthesis, 224, 358 Pyrylium salt synthesis, 24 Q Quinazolone synthesis, 345 Quinodimethane synthesis, 319b Quinoline synthesis, 76, 93b, 128b, 167t, 261b, 375b, 404, 443b Quinolizidine synthesis, 201t Quinone synthesis, 482b R Radical dehalogenation, 275 Rearrangement, 7, 9, 16, 23, 39, 60, 62, 78, 82t, 87, 92t, 104, 107t, 122b, 149, 153b, 165–166, 208, 227, 230, 240, 254, 294, 311t, 323b, 325, 336, 414, 420b, 426, 443t Rearrangement benzylic, 290t Rearrangement catalytic, 16, 39, 78, 79t, 107t, 167–168, 315–316, 366, 412, 458–459, 515–516 Rearrangement hetero (3, and 3, 5), 437 Rearrangement intramolecular, 208–209 Rearrangement photochemical, 325–326 Rearrangement sigmatropic, 5, 97, 195, 233, 259–260, 272, 323–324, 346–347, 359, 525–526, 543–544 Rearrangement stereoselective, 366 Rearrangement thermal, 79, 225, 325–326, 426–427, 437 Redox reaction, 77 Reduction, 46t, 57b, 82b, 90, 295, 310, 353t, 453, 529 Reduction enantioselective, 98 Reduction regioselective, 353, 470 Reductive amination, 55, 287t, 293–294 Reductive condensation, 138t Reductive cyclization, 466 Reductive elimination of C¼O, 75b Reductive iodination, 255–256 Reductive nitroarene alkylation, 407b Regiospecific synthesis, 302 Resolution optical, 381 Rh Allylic oxidation, 495 Ring closure, 205 Ring contration, 528–529 Ring enlargement, 7–8, 12–13, 71–72, 86–87, 375, 459, 484–485 Ring expansions, 52b, 313, 510 Ru heterocyclization, 510b S Salicylic acid synthesis, 267t Selective diol oxidation, 332 Selectively subsituted alkene synthesis, 264 Selective metal-free hydrogenation, 293 Selective reduction, 55, 211–212, 295, 322, 353, 472–473, 515t Selenium dioxide oxidation, 401 Silaketone rearrangement, 62 Siloxy-heterocycle coupling, 478 Silyl chloride synthesis, 160t Solid state reaction, 486 Stereoselective alkene synthesis, 100b Stereoselective allylation, 220 Stereoselective hydroxylation, 480t Stereoselective reducing agents, 68 Stilbene synthesis, 440t Substitution, 181–182, 323t, 417t, 497b Sugar homologation, 258 Sugar oxidation, 451 Sulfide contraction, 143t Sulfoxide glycosidation, 249t Sulfoxide rearrangement, 323b, 389 Supersilyl sequential aldol, 535 T Tandem reaction, 484t Tetrazole synthesis, 155t Thermal cycloadditions, 53t Thiacarbonylation, 283 Thiacarbonylation reagent, 283 Thiazoline synthesis, 13 Thiocyclization, 153t Thioester C-C coupling, 171 Thioester coupling, 289 Thiophene synthesis, 217, 504b Thiophenol synthesis, 165b, 287b Tosylation, 269t Tosylhydrazone decomposition, 27b Triazole synthesis, 127, 160b Trifluoromethylation, 74, 412–413, 487 Trifluoromethyloxazole synthesis, 254 Trioxane synthesis, 384t V Vicarious nucleophilic substitution, 298b Vinylcyclopentane synthesis, 151t Vinylhalocyclopropane rearrangement, 443 Vinyl phosphate synthesis, 371t X Xanthate elimination, 85 Y Ylide rearrangement, 448t Z Zipper reaction, 63b ZIP reaction, 214b Z-Olefin synthesis, 94b, 462t 571 Functional Group Transformation Index To Ỉ Alkanes, Cyclo-alkanes Alkenes Alkynes Alkanes, Cycloalkanes 124, 432 38, 240 Alkenes, Alkynes 32, 102, 105, 113, 121, 124, 125, 135, 151, 152, 181, 194, 195, 246, 273, 275, 278, 291, 293, 302, 329, 349, 357, 363, 375, 441, 452, 470, 490, 515, 542 7, 32, 38, 46, 57, 72, 82, 93, 94, 100, 106, 108, 109, 117, 120, 125, 135, 171, 173, 182, 183, 243 Aryls 362 46, 311, 319, 440 Halogen compounds 81, 165, 172, 205, 255, 94, 192, 221, 260, 306, 275, 353, 363, 441, 324, 443, 461 465, 490 168, 435, 449, 457 Alcohols 36, 333 342 Aryls, Polyaryls Halogen Compounds 30, 430 528 6, 42, 63, 159, 185, 210, 334, 399 32,86, 204, 206, 302, 385, 432 From Ø 73, 85, 103, 174, 189, 257, 302, 304, 480 63, 185, 399 18, 20, 50, 159, 186, 262, 303, 410 206, 208, 253, 266, 290, 334, 378, 388, 422 237 Phenols 74, 94, 155, 159, 328, 357, 412, 467, 474 10, 505 20, 237 196 264 Ethers Quinones 289 B compounds S, Si, Sn, P, As, Bi Compounds 50, 181, 219, 277, 303, 323 205, 491 143, 228, 241, 242, 391, 415, 462 219 Nitro, Nitroso, Azo, Hydrazo, Azoxy, Azides 305 14, 305, 417 341, 417, 420 Amines 33, 180 97, 222 237 186, 190, 237, 305, 388 Organometallic Compounds 105, 156, 179, 291, 357, 470, 490 105, 192, 210, 260, 263, 264, 291, 415, 461 342, 449 158, 206, 277 Aldehydes 190, 255, 521 103, 176, 228, 241, 242, 261, 307, 462, 467, 477, 524 101, 241, 352 292, 412 Ketones 199, 529, 75,90, 46 141, 253, 372, 373, 433, 481, 35,91,176, 132, 138, 198,199, 253, 313, 481, 43 93, 432 137, 208 3, 455 Acids, Anhydrides, Esters 196, 276 111, 124, 135, 167, 169, 171, 183, 463, 492 232 34, 108, 211, 232, 263, 445 59, 206, 496 Amides, Amidines, Nitriles Amino acids, Peptides Miscellaneous Including Heterocycles 501 197, 323 574 Functional Group Transformation Index To Ỉ Alcohols Alkanes, Cycloalkanes 195, 491 Alkenes, Alkynes 96, 209, 220, 273, 274, 320, 343, 355, 384, 385, 419, 435, 491 Phenols, Thiophenols Ethers, Quinones, Epoxides B Compounds From Ø 58, 111, 137 Aryls Halogen compounds 65 Alcohols 324 Phenols Ethers Quinones 111, 117, 124, 169 B compounds 145, 221, 355, 446 S, Si, Sn, P, As, Bi Compounds 323, 330, 480 Nitro, Nitroso, Azo, Hydrazo, Azoxy, Azides S, Si, Sn, P, As, Bi Compounds 131, 235, 239, 311, 386, 436 209, 432 489 153 114 11, 14, 406 116 116, 304, 366, 368, 390, 446 32, 165, 196, 229, 303, 341, 544 131, 413, 450, 482 158, 124 178 38, 61 364, 446 4, 62, 89, 112, 160, 259, 308, 319, 323, 347, 388, 389, 452, 455 437 455 287 37, 94, 100, 251, 252, 287 Amines 122 Organometallic Compounds 30, 55, 88, 121, 153, 159, 179, 194, 273 Aldehydes 1, 2, 77, 81, 134, 146, 147, 190, 212, 220, 221, 225, 228, 282, 296, 322, 327, 330, 335, 346, 363, 412, 415, 429, 515 Ketones 1, 6, 65, 66, 68, 69, 98, 111, 138, 145, 170, 211, 225, 295, 296, 310, 318, 349, 355, 374, 429, 446, 466, 498, 530 5, 16, 207, 325, 483 27, 62, 347 Acids, Anhydrides, Esters 56, 276 207 Amides, Amidines, Nitriles 147 452 114, 256, 354 2, 38 13, 283, 353, 522 309, 379, 445 34, 504 14 Amino acids, Peptides Miscellaneous Including Heterocycles 200, 282, 478, 350 7, 499 Functional Group Transformation Index Nitro, Nitroso, Azo, Hydrazo, Azoxy, Azides Amines, Imines Organometalic Compounds 575 Aldehydes Ketones 430 137, 145, 405 498 216, 425, 434 203, 250, 274, 286, 315, 405, 503 67, 115, 203, 206, 250, 274, 357, 365, 412, 454, 498, 507 55, 133, 136,137 166, 281 203, 250, 460, 524 314 448 281, 482 73, 122, 173, 204, 308, 314, 43 327, 438 1, 40, 52, 77, 92, 107, 268, 305, 397, 406, 447, 460 9, 324, 504 79, 106, 123, 129, 239, 267, 100, 102, 106, 129, 158, 286, 288, 376, 475 239, 315, 331, 332, 344, 355, 418, 475, 482, 484, 488, 542 38, 196 164 346, 444 4, 4, 229 112 179 87 305 425, 427 28, 35, 212, 311, 472, 17, 57, 109, 135, 136, 407, 482 453, 493, 536 119, 134 143, 171 337 71, 203, 540 63, 126, 144, 163, 214, 216, 225, 237, 312, 354, 357, 369, 371, 458, 459 425 161 429, 500 464 92, 460 431, 432, 486, 494 55, 70, 287, 301 258, 400, 460 71, 409, 457, 464, 484 55, 114, 138, 186, 287, 292, 353, 504 487, 448 29, 132, 138, 292, 317, 319, 348, 401, 403, 415, 457, 463, 464, 513 308, 406, 452 48, 50, 79, 80, 88, 111, 124, 135, 167, 169, 171, 183, 289, 431, 452, 494, 512 43, 59, 218, 223, 249, 333, 362, 412, 472 448, 456, 511 450 84, 478 311, 316 409, 489 109, 114, 294 216, 327, 406, 439 233-234 438 576 Functional Group Transformation Index To Ỉ Acids, Anhydrides, and Esters Amides, Amidines, Nitriles, and Lactams From Ø Hydroxy- aldehydes, Ketones, Acids, Phenols, and Sugars Amino acids, and Peptides 314 Alkanes, Cycloalkanes 300 Alkenes, Alkynes 170, 262 259, 329 Aryls 170, 369 298 Halogen compounds 31, 274 29, 407 156 Alcohols 123, 129, 262, 331, 455 182, 321 9, 178 Phenols 128 82, 143, 445 11, 133, 137, 229, 396 Ethers Quinones 154, 165 B compounds S, Si, Sn, P, As, Bi Compounds 102, 171 Nitro, Nitroso, Azo, Hydrazo, Azoxy, Azides 399, 476 39, 314, 420 17 226 Amines 252 8, 223, 251 223, 251 226, 351, 422, 495, 522, 530, 533 Organometallic Compounds 193 445 Aldehydes 10, 77, 121, 261, 380, 389, 462, 485, 486 10, 40, 321 1, 6, 79, 146, 258, 279, 292, 40, 139, 351 356, 395, 411, 535 Ketones 149, 274, 290, 300, 468, 476, 533 420, 498, 499 6, 107, 119, 199, 290, 330, 414, 469, 502 Acids, Anhydrides, Esters 12, 30, 102, 107, 162, 188, 198, 211, 238, 243, 270, 369, 392, 408, 455, 462 182, 436 1, 384 114, 57 Amides, Amidines, Nitriles 104, 221 175, 467, 510 469 114, 469, 508 213, 438, 495 Amino acids, Peptides Miscellaneous Including Heterocycles 316 153, 451 351, 422 Functional Group Transformation Index 3,4,5- Ring, Heteroatoms 22, 152, 204, 215, 235, 239, 308, 361, 364, 386, 387, 410, 418, 436 Heterocycles 3,4,5- Ring, 6,7-and Large or more Ring Heteroatoms Heteroatoms 72, 418 19, 280 150, 221, 342 60, 113, 215 Miscellaneous and Including Heterocycles 130 261 202 237, 304 342 Nucleosides Other Heterocycles 577 174 268, 383 366 158 216 114 23, 342, 366, 403, 442, 497 153 265 419 176, 179, 217 426 19, 75, 221, 259, 285, 407, 423, 455 231, 367, 418 44, 46, 75, 284, 378, 398 47, 117, 128, 167, 177, 186, 218, 224, 225, 358, 361, 416, 513 22, 26, 50, 192, 214, 490 43, 167, 177, 187, 218, 26, 93, 128, 178, 195, 224, 225, 285, 337, 345, 404, 416, 495, 339, 383, 404, 443, 496, 526 459, 495, 510, 539 114, 120, 215, 259 130, 140, 158, 421 44, 81, 83, 113, 157, 167, 201, 284, 392 421 114 92, 99, 109, 150, 157, 217, 364, 407 13, 45, 61, 70, 116, 202, 235, 405, 499 24, 201, 403, 440 13, 178, 546 197 111, 231, 418, 423 117, 280 504 366 179, 182, 298 127, 158, 160, 187, 192, 511 61 140 27, 51, 84, 88, 138, 173, 174, 176, 297, 366 56, 230, 299, 326 52, 76, 249, 298 261, 377, 398, 405, 490 3, 7, 15, 17, 53, 59, 201, 279, 297, 312 197, 224, 312, 328, 408 216, 346, 505 7, 192, 197, 200, 230, 279, 299, 326, 370, 375, 408, 509, 537 .. .Organic Syntheses Based on Name Reactions A Practical Guide to 750 Transformations Third Edition A Hassner, Bar-Ilan University, Israel I Namboothiri, IIT Bombay, India Amsterdam • Boston... Leuckart–Pictet–Hubert (phenanthridine); List-MacMillan (dihydropyridine C¼C hydrogenation); Mukaiyama (lactonization w halopyridinium); Meerwein (O-alkylation); Mukaiyama (lactonization w halopyridinium);... fluorination); Swarts (Cl to F); Togni (electrophilic CF 3); Vorbruggen (OH to F) An Overview of Synthesis Related Name Reactions xxiii Free Radical Reactions: Barton (deamination); Barton (nitrite