mundy - name reactions and reagents in organic synthesis 2e (wiley, 2005)

NAME REACTIONS AND REAGENTS IN ORGANIC SYNTHESIS Second Edition Bradford P. Mundy Prof. of Chemistry, Emeritus Colby College Waterville, ME Michael G. Ellerd Maxim Technologies Bozeman, MT Frank G. Favaloro, Jr. Helicon Therapeutics Farmingdale, NY WILEY- INTERSCIENCE A JOHN WILEY & SONS, INC., PUBLICATION This Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left Blank This page Intentionally Left Blank NAME REACTIONS AND REAGENTS IN ORGANIC SYNTHESIS This Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left BlankThis Page Intentionally Left Blank This page Intentionally Left Blank NAME REACTIONS AND REAGENTS IN ORGANIC SYNTHESIS Second Edition Bradford P. Mundy Prof. of Chemistry, Emeritus Colby College Waterville, ME Michael G. Ellerd Maxim Technologies Bozeman, MT Frank G. Favaloro, Jr. Helicon Therapeutics Farmingdale, NY WILEY- INTERSCIENCE A JOHN WILEY & SONS, INC., PUBLICATION Copyright 0 2005 by John Wiley & Sons, Inc. All rights reserved. Published by John Wiley & Sons, Inc., Hoboken, New Jsersey. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocop:ying, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the publisher, or authorization throsugh payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923,978-750- 8400, fax 978-646-8600, or on the web at www.coPyright.com. Requests to the publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 11 1 River Street, Hoboken, NJ 07030. (201) 748-6008, fax (201) 748-6008. Limit of LiabilitylDisclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular piurpose. No warranty may be created or extended by sales representatives or written sales materia.ls. The advice and strategies contained herin may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be lialble for any loss of profit or any commercial damages, including but not limited to special, incidental, consequential, or other damages. For general information on our products and services contact our Customer Care Department within the U.S. at 877-762-2974, outside the US. at 317-572-3993 or fax 317-572-4002. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print, however, may not be available in electronic format. Library of Congress Cataloging-in-Publication Data is available. ISBN 0-471-22854-0 Printed in the United States of America 10987654321 Preface It has been a long haul. The start for this revision came almost the same way that the original edition started. For the fnst edition it was Mike Ellerd, then an undergraduate at Montana State, who organized my crude Name Reaction handouts so well that others encouraged the conversion into a book. At Colby College, Frank Favaloro did the same thing, making “study sheets” and adding to the list of Name Reactions. He graduated in 1996 and I started reformatting and expanding. With encouragement from Darla Henderson, this became a project. By then Frank had finished graduate school and was enthusiastic about participating. I had also retired from formal teaching and found much more time for creative work. The three of us started to work in earnest! This edition differs substantially from the fmt by the inclusion of many modem Name Reactions instead of sticking exclusively with the old, tried and true. There are many reactions not covered; indeed, we ultimately eliminated those that had little contemporary use. We generally applied a “rule of thumb” that a newer name had to be cited by multiple authors. Therefore there are some relatively new protocols that have not stood the test of time; however the breadth of recent use warranted inclusion. As for reagents, we have focused on both Name Reagents and those whose acronyms are often used in place of the actual name. We have noted the common use of these forms in current literature. First and foremost, this is a book to be used. Feel free to write in the text. . . use any available blank space to add your own notes. Transform this intoyow book of Name Reactions! It is intended to serve as a starting point. Within a two page format for reactions and one page for reagents, the reader will fmd a basic, generalized defmition / formula, a mechanism that conveys a possible course from starting material to product, notes which describe a few of the major highlights of the reaction or which points the reader to related reactions (by name or similarity) and recent examples of use. We have tried to convey the current mechanistic thinking with special care to show intermediate steps, point out proton exchanges, and sometimes suggest transition states, but without going through kinetics, isotope effects, etc. Wherever appropriate, we have included references to selected secondary sources. They contain more detailed discussions on the topics introduced in this book. In all cases, we recommend use of the primary literature. The examples in the following pages are but a small taste of the detail, variation, scope and experimental detail available. Our choices reflect our personal interests; there is no “better or worse” implied! We tried to use current examples from journals that seem to be most commonly accessible, both in paper form and electronically, to student and professional alike. When recent references were difficult to come by, we made use of the abstracts and reaction-search engine of SciFinder (American Chemical Society). In these cases, we supplied a number [AN year: XXXX] that will allow ready access to the abstract. To the authors of the works we have chosen to describe, we hold the most sincere gratitude and we hope we have faithfully represented your work. Colby College Waterville, ME Feb 1,2005 ACKNOWLEDGMENTS As always, completion of a project requires more than just the work of the authors. Without the consideration, support and patience of spouses: Margaret (Brad), Mary (Mike) and Michelle (Frank), this probably could not have been completed. methods for creating C-C and C-heteroatom bonds. It has been an enlightening experience to chronicle the explosion of new “named” reactions and protocols. We have not lost view of the obvious new participation of the world chemical community. Each of us can thank mentors and spe’cial people that have given us encouragement: Special thanks goes to the chemistry community for their endless development of new Brad: I still owe much to my formal mentors: Richard F. Smith who first provided the excitement of chemistry, A.Paul Krapcho, graduate mentor and friend, and the late Henry Rapoport, postdoctoral advisor. help in reading parts of this manuscript. And, of c:ourse my former graduate and undergraduate students . . . two of the latter are now coauthors, who were the reason for my continued interest in the academic life. Special thanks goes to Prof.Tom Poon (Claremont McKenna, Pitzer, & Scripps Colleges) for a great two years as a Dreyfus Fellow with me at Colby. He taught me much, and worked closely with Frank Favaloro. the Science Library could always be depended on to solve any library problem that developed in the absolutely great electronic resources of Colby College, and patiently put up with my many requests, piled up books and journals and general use of the library. The Colby College ITS staff was extremely good-natured and helpfd for computer questions. Their help was greatly appreciated. Mike: My appreciation goes out to all of my professors at Montana State, who,years ago sparked my interest in chemistry, and to those who still today keep that interest very much alive. Frank: I would like to thank all of those who not only taught me organic chemistry, but also to be excited for the art it contains: Gordon W. Gribble, Tadashi Honda, Thomas Spencer, Peter Jacobi, David Lemal, Thomas Poon, Philip Previte and, most i,mportantly, Brad Mundy. Thank you to the many friends and co-workers who provided support, advice and the occasional reference: Erin Pelkey, Janeta Popovici-Muller, Tara Kishbaugh, Jeanese Badenock, Alison Rinderspacher and Chaoyang Dai. I thank my colleagues from Colby College, Dasan Thamattoor and Jeff Katz, for their I would like to thank several Colby staff that made my working easier: Susan W. Cole of Of course a project with a publisher requires interaction. Darla Henderson, Amy Byers, Camille Carter and Dean Gonzalez were the peoplle who kept the ball rolling and the project in focus. Colby College Waterville, ME Feb 1,2005 vi CONTENTS Acronyms and Abbreviations / viii NameReactions / 1 Name Reagents and Acronyms / 714 Index /872 vii ACRONYMS AND ABBREVIATIONS Acronvm Ac Acac AcOH (HOAc) AIBN ACN BZNAP BZNOL BITIP Name Acetyl Acetylacetonate Acetic acid 2,2’-Azobisisobutyronitrile 1,l ’-Azobis- 1-cyclohexanenitrile 9-Borobicyclo[3.3. llnonane 2,2’-Bis(Diphenylphosphino)-l, 1 ’- binaphththyl 1,l ’-bi-2,2’-naphthol BinolKitanium isopropoxide Bromomagnesium Diisopropylamide Borane Dimethylsulfide Me Me Me -COOH NC+- N= N- LCN \ Me Me H A Ti(iPr0)4 / BINOL BH3-Me2S viii [...]... Ph-N-Me \ Me 0 Br3 " Acronyms and Abbreviations Me Pyridinium para-toluenesulfonate p-Toluenesulfonic acid; rosic acid Pv Pivaloyl Pyridine (R )-1 -Amino-2Methoxymethylpyrrolidine (S )- 1-Amino-2Methoxymethylpyrrolidine Ender's Reagent 2-Trimethylsilylethoxy-methoxy SEM Me, Me' SMEAH Me I Si -0 42 Sodium Bis(2methoxyethoxy)aluminum Hydride Tetrabutylammonium fluoride TBDPS tert-Butyldipheny lsilyl Ph t-Bu... Me Me -S-Me 1: DNP 1,2-Bis(diphenyIphosphino)ethane (DIPHOS) Ph-P I Ap-ph Ph Ph-P pi I P-Ph I Ph n Ph ee enantiomeric excess = % major enantiomer - % minor enantiomer Fmoc 9-Fluoren ylmethoxycarbonyl Acronyms and Abbreviations xii 2-( 6-Chloro- 1H-benzotriazole- 1-yl)1,1,3,3-tetramethyIuronium hexafluorophosphate 0 0 Hexamethylphosphoric triamide Me N’ Me I Hexamethylenetetramine Hydroxy(tosy1oxy)-iodobcnzene... triethylenediamine Me 3 HO,S-H, Acronyms and Abbreviations Diethylamino)sulfur trifluoride Et, N -SF, Et) Dicyclohexylcarbodiimide 2,3-Dichloro-5,6-dicyano1,4benzoquinone NC Nc+ CI 0 Me Dimethyldioxirane Me Diethyl Azodicarboxylate DEIPS EtOOC-N=N-COOEt Diethylisopropylsilyl Et i-Pr -hi E( -$ YH DET Dietkyl tartrate EtOOC -CHCH-COOEt I HO in R-, S, and meso forms DZBAL DZBAL-H Disobutylaluminum hydride... \Si Ph' -5 t-Butyl hydroperoxide TBS TBDMS tert-Butyldimethylsilyl TEA Triethylamine TEBA TEBAC Benzyltriethylammonium chloride TEMPO 2,2,6,6-Tetramethylpiperidin- 1-oxyl 0 xv cronyms and Abbreviat ns Et TES Triethylsilyl Tf Triflate THF Tetrahydrofuran THP Tetrah ydropyranyl TIPS Triisopropylsilyl i-Pr ‘ -2 i-Pr -Si i-Pr’ TMEDA N,N,N’,N - n Tetramethylethylenediamine Me-” I Me TpAP Tetra-n-Propylammonium... IcLI~BH -3 LN Diisopinocampheylborane Lead tetraacetate h ?Ac AcO -Pb -0 Ac I OAc LTMp LiTMP Lithium 2,2,6,6tetramethylpiperidide Methylaluminum bis(2,6-di-t-butyl4-methylphenoxide) I MCPBA m-Chlorperoxybenzoic acid F Acetonitrile 2-Methoxyethoxymethyl Ms Mesyl ,Methanesulfonyl Me-CzN xonyms and Abbreviat ns Methylthiomethyl WTM Xlll ~~ WVK Methyl Vinyl Ketone N-Bromosuccinimide OQO I Rr N-Chlorosuccinimide... complete in showing steps, intermediates and the necessary curly arrow notations Notes: Additional comments and references from key sources Examples: Current examples if possible When a term is underlined, (for example, AIdol Condensation) it means that the concept can be found under an independent heading in the book General Bibliography: B P Mundy, M G Ellerd, Name Reactions and Reagents in Organic Synthesis, ... John Wiley and sons, Inc., New York, 1988; M B Smith, J March in March's Advanced Organic Chemistv, 51h ed., John Wiley and Sons, Inc., New York, 2001; T Laue, A Plagens, Named Organic Reactions, John Wiley and Sons, Inc., New York, 1998; V K Ahluwalia, R K Parashar, Organic Reaction Mechanisms, Alpha Science International Ltd., Pangbourne, U.K., 2002; J J Li, Name Reactions, Springer, Berlin, 2002;... Comprehensive Organic Synthesis, B M Trost, editor -in- chief, Pergamon Press, Oxford, 1991; M B East, D J Ager, Desk Referencefor Organic Chemists, Krieger Publishing Company, Malabar, FL, 1995; M Orchin, F Kaplan, R S Macomber, R M Wilson, H Zimmer, The Vocabulary of Organic Chemistv, John Wiley and Sons, Inc., New York, 1980; A Hassner, C Stumer, Organic Syntheses Based on Name Reactions and UnnamedReactions,... Syntheses & Arens-van Dorp Cinnamaldehyde Synthesis RO R Lindar Reduction * y+OEt OEt -0 Et OEt R acetal 0 R O - Bodrozu-Chichibabin Aldehyde Synthesis OEt J-\RMgX OH 0 - EtOH Et Bouveault Aldehyde Synthesis DMSO-based Oxidations Albright-Goldman Oxidation / Albrieht-Goldman Reapent 11 Name Reaction Corey-Kim Oxidation / Corm-Kim Reaeent NCS N-ChloroSuccinimide Kornblum Aldehvde Svnthesis 1.AgTs R $H 2.DMSO... Organic Chemistry, 51h ed., John Wiley and Sons, Inc., New York, 2001, p 1562; T Laue, A Plagens, Named Organic Reactions, John Wiley and Sons, Inc., New York, 1998, pp 1-3 ; S M McElvain, Organic Reactions, 4,4; J P Schaefer, J J Bloomfield, Organic Reactions, 4, 15; J J Bloomsfield, J M Owsley, J M Nelke, Organic Reactions 23,2 The Riihlmann modification (Bouveault-Blanc Condensation or Ruhlmann Reaction) . EtOOC-N=N-COOEt Et i-Pr -hi -$ E( YH EtOOC -CHCH-COOEt I HO in R-, S, and meso forms Me Me $1 Me h dMe Me Me ( Me Me-(NJ Me OH iPrOOC -CHCH -COOiPr I I HO in R-, S, and. Me -S-Me 1: A Ph-P p-ph Ph pi I n Ph-P P-Ph II Ph Ph Acronyms and Abbreviations xii I IcLI~BH r LTMp LiTMP I MCPBA F Ms 2-( 6-Chloro- 1H-benzotriazole- 1 -yl )- 1,1,3,3-tetramethyIuronium. Acetic acid 2,2’-Azobisisobutyronitrile 1,l ’-Azobis- 1-cyclohexanenitrile 9-Borobicyclo[3.3. llnonane 2,2’-Bis(Diphenylphosphino)-l, 1 - binaphththyl 1,l ’-bi-2,2’-naphthol BinolKitanium