Volume 10 the total synthesis of natural products

THE TOTAL SYNTHESIS OF NATURAL PRODUCTS Edited by David Goldsmith Department of Chemistry Emory University Atlanta, Georgia THE TOTAL SYNTHESIS OF NATURAL PRODUCTS Volume 10 A Sesquidecade of Sesquiterpenes: Total Synthesis, 1980-1994 Part A: Acyclic and Monocyclic Sesquiterpenes Michael C Pirrung and Andrew T Morehead, Jr Department of Chemistry Duke University Durham, North Carolina A Wiley-Interscience Publication JOHN WILEY & SONS, INC NewYork Chichester Weinheim Brisbane Singapore Toronto This text is printed on acid-free paper Copyright 1997 by John Wiley & Sons, lnc All rights reserved Published simultaneously in Canada Reproduction or translation of any part of this work beyond that permitted by Section 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012 Library of Congress Cataloging in Publication Data: CIP data available ISBN 0-471-59679-5 CONTENTS Introduction Reagent Glossary I ACYCLIC SESQUITERPENES Acknowledgments A Farnesene Farnesol Terrestrol B Nerolidol 5.8.Dehydro 4.oxonerolidol C Sesquilavandulol D Solanone E Sinensals F Juvenile Hormones G 2.5.9.Trimethyl.2.vinyl.deca.4.8.dienal (I9.6.1O.Dimethyl methylene-undec-5-en-2-one ix xi xv 13 H Dendrolasin, Sesquirosefuran,Freelingnite Dehydrolasiosperman, Dehydromyopyrone, (R).Myopyrone Pleraplysillin.2 Siphonidictidine I Ipomeamarone Davanone Artemone Athanasin 14 20 References 25 II MONOCYCLIC SESQUITERPENES A Aromatic Bisabolenes a.Curcumene, iso.a.Curcumene ar-Turmerone Nuciferol, Nuciferal Curcuquinone Curcuphenols Curcudiol Perezones Xanthorrhizol ar-Todomatuic Acid ar.Juvabione Elvirol Sydonic Acid Hellianuol A Furoixiolal B Bisabolenes a.Bisabolene P.Bisabolene y-Bisabolenes 29 29 29 36 39 43 44 45 45 V vi Contents Epoxy.a.bisabolene, Bisabol- lO.ene.3.7.oxide y-Bisabolene8.9.oxide 4.5.Dihydro.P.curcumen.4 5.diol a.Bisabolo1 P.Bisabolo1 a.Atlantone P-Atlantone Aminobisabolene Theonellin Isocyanide 8-Desoxyisocaespitol Zingiberenol P.Sesquiphellandrene Bilobanone Bisabolangelone Lanceol Hernandulcin Juvabiols Juvabione Paniculides Phyllanthocin Phyllanthocindiol Phyllanthoside C Elemanes P.Elemene y.Elemene a.Elemene P.Elemo1 P-Elemenone Shyobunone Curzurenones Melitensin Deoxymelitensin Temisin Saussurea Lactone Zempoalins Callitrin Igalan Isogermafurenolide Isofuranogermacrene Hydroxyisogermafurenolide Desoxysericealactone and Unnamed 1ZElemanolides Vernolepin D Peroxidic Antimalarials Qinghaosu (Artemisinin) Yingzhaosu A Yingzhaosu C E Cyclocitrals Deoxytrisporone (E).3.Formyl.(2.6.6.trimethyl.2.cyclohexenyl ) 3.pentenal 4.(2.2.6.trimethyl.6.vinylcyclohexyl) 2.butanone Caparappi Oxide Dactyloxene-B and C Ancistrofuran Ricciocarpin Pallescensin Penlanpallescensin Snyderols Aplysistatin Palisadins F Secoeudesmanes Phytuberin Eriolanin Eriolangin Tridensone Umbellifolide G Germacranes Germacrene.D Bicyclogermacrene Isobicyclogermacrenal Hedycaryol Acoragermacrone Germacrone Costunolide Dihydrocostunolide Haageanolide Isabelin Eucannabinolide 4.5.cis.3b.Hydroxygermacranolide Aristolactone Linderalactone Neolinderalactone Sericenine Periplanones H Miscellaneous Monocarbocyclic Sesquiterpenes Humulene Zerumbone Bicyclohumulenone 50 53 55 57 60 62 67 71 77 78 84 85 85 88 90 90 97 98 99 103 104 108 108 110 112 114 114 116 118 124 125 129 129 Contents Furoventalene Pleraplysillin-1 Myodesmone Myomontanone Lactaral Hanegokedial Heptelidic Acid Ovalicin Curcumanolide A Isocanambrin Methyl Acorate Secocrispiolide Himasecolone Methyl Nidorellaurinate Sesquichamaenol 3-Methyl-5-(2.3.6-trimethylphenyl )- 1-penten-3-01 Karatavic Acid Cabreuva Oxides Isohumbertiols Chokol C References AuthorIndex SubjectIndex SkeletonIndex vii 134 138 140 143 145 146 148 150 161 163 166 ACKNOWLEDGMENTS In any large effort such as this, contributions are made by many beyond those whose names appear on the masthead David Goldsmith was an extremely supportive and insightful editor Kitty Porter provided great assistance in the literature search Financial support for the preparation of this monograph came from Abbott Laboratories, Firmenich, Hoechst-Roussel, Hoffman-La Roche, IFF Foundation, McCormick, Merrell Dow Pharmaceutical, Robertet, Sunkist Growers, Syntex, USA, and Zeneca I greatly appreciated the solitude provided by the Baylor College of Medicine and the Dyson Perrins Laboratory of the University of Oxford and the hospitality of C T Caskey and J E Baldwin during the preparation of this portion of the manuscript Financial support during these leaves came from the John Simon Guggenheim Memorial Foundation and the Burroughs Wellcome Fund Finally, we would like to acknowledge our intellectual debt to Clayton Heathcock, whose previous contributions to this series have set a high standard which we can only hope to approach Michael Pirrung Durham, North Carolina INTRODUCTION The total synthesis of sesquiterpenes has been an exploding field of research in organic chemistry over the last fifteen years When it was last reviewed, in Volume of this series,' syntheses of over 250 different target molecules were reported in over 500 papers published during a ten-year period In the most recent fifteen years, the number of sesquiterpenes synthesized grew to over 500; this reflects the aggregate of over 1600 papers Modem technology was therefore essential for the preparation of this monograph; the on-line version of Chemical Abstracts was crucial to the comprehensive collection of citations While efficient, the computer search of the literature was certainly not foolproof; however, responsibility for omissions lies only with the authors Our search did enable us to prepare a database of the most recent sesquiterpene total synthesis literature that has been annotated by skeletal class, key reaction, and stereochemical traits of each synthesis We are pleased to make this resource available to those who are interested The review is organized, as in its earlier incarnations, by the number of carbocyclic rings in the target: acyclic, monocyclic, bicyclic, and tricyclic, not including cyclopropane rings Compounds containing these are included with the skeletal class to which the compound without the cyclopropane ring would belong, since they usually represent a simple alternative 1,3-proton loss in the biosynthetic pathway to the parent Often, the synthetic routes to these targets are based on the preparation of the parent skeleton and straightforward cyclopropanation This policy guards against dispersion of conceptually related syntheses For the most part, multiple syntheses of the same compound are presented in chronological order Because of the size of this literature, we have broken the work into chapters based on the ring systems, unlike the earlier versions Sesquiterpene syntheses have also grown beyond the limits of a single volume in the Total Synthesis of Natural Products series We thought it intellectually most satisfying and logical to group the chapters by increasing complexity, leading to this smaller volume of acyclic and monocyclic targets and a much larger volume of bicyclic and tricyclic sesquiterpenes to be presented shortly xi xii Introduction Relatively simple, commercially available starting materials must be used if a work is to meet our definition of a total synthesis If another sesquiterpene is the starting material, a change of the carbon skeleton must occur for the synthesis to qualify for inclusion It has been interesting to see the overall progress in organic synthesis reflected in this relatively narrow area of sesquiterpenes The most dramatic change in the past fifteen years has been the significant increase in the numbers of targets that have been prepared in optically active form In providing legends for the schemes, syntheses of racemates are not specifically marked Those producing optically active compounds include either their absolute configurations, signs of optical rotation, or both Each scheme is identified by the senior author or the institution at which the work was conducted This policy is not intended to underemphasize the contributions of junior authors to the work It is also necessary to mention the efforts of others who have reviewed parts of this field in the last fifteen years There is a comprehensive compilation of the furanosesquiterpene literature.2 Several workers have discussed the burgeoning field of polyquinane ~ y n t h e s i s Two ~ ~ short ~ , ~ reviews ~ ~ ~ ~ have covered the area of the artemisinin antimalarial agents.* The synthesis of sesquiterpenes from santonin has been s ~ m m a r i z e d , as ~ have syntheses of hydroazulene sesquiterpenes via rearrangement of hydronaphthalenes.10 The synthesis of drimane and clerodane insect antifeedants, bisabolones,12 and the trichothecenes have all been summarized.l General reviews of sesquiterpenoid synthesis have also appeared.14 References C H Heathcock, S L Graham, M C Pirrung, F Plavac, and C T White, in The Total Synthesis of Natural Products, Volume5, edited by J ApSimon, John Wiley & Sons, Inc., New York, 1981 A J Allen, V Vaillancourt, and K F Albizati, Org Prep Proc Intl., 26, 1-84 (1994) D P Curran, Adv Free Radical Chem., 1, 121-157 (1990) X Fu and J M Cook, Aldrichimica Acta, 25, 43-54 (1992) T Hudlicky, F Rulin, T C Lovelace, and J W Reed, Stud Nut Prod Chem 3, 3-72 (1989) J Mulzer, Org Synth Highlights, 323-334 VCH: Weinheim (1991) L A, Paquette, Stud Nut Prod Chem., 13, 3-52 (1993) T Ravindranathan, Cum Sci., 66, 35-41 (1994) W.4 Zhou and X.-X Xu, Acc Chem Rex, 27, 211-216 (1994) A K Banerjee, W J Vera, and G N Canudas, Tetrahedron, 49, 4761-4788 (1993) 10 L H D Jenniskens, J B P A Wijnberg, and A De Groot, Stud Nut Prod Chem., 14, 355-387 (1994) 11 A De Groot and T A Van Beek, Recl Truv Chim Pays-Bas., 106, 1-18 (1987) B J M Jansen and A De Groot, Nut Prod Rep., 8, 319-337 (1991) Monocyclic Sesquiterpenes 159 209 H Shirahama, K Hayano, Y Kanemoto, S Misumi, T Ohtsuka, N Hashiba, A Furusaki, S Murata, R Noyori, and T Matsumoto, Tetrahedron Lett., 21,4835-8 (1980) 210 T Takahashi, Y Yamashita, T Doi, and J Tsuji, J Org Chem., 54,42735 (1989) 211 Y Fukuyama, M Hirono, and M Kodama, Chem Lett., 167-170 (1992) 212 F Kido, Y Noda, T Maruyama, C Kabuto, and A Yoshikoshi, J Org Chem., 46,4264-4266 (1981) 213 D E Bergstrom and P A Reddy, J Heterocyclic Chem., 20,469 (1983) 214 H Hagiwara and H Uda, J Chem SOC.Perkin Trans 1,91-94 (1984) 215 R Castanedo, C B Zetina, and L A Maldonado, Heterocycles, 25, 175178 (1987) 216 F Bohlmann and G Fritz, Tetrahedron Lett., 22,95-96 (1981) 217 F Bohlmann and G Fritz, Tetrahedron Lett., 22,4803-4806 (1981) 218 H Liu, L M Gayo, R W Sullivan, A Y.H Choi, and H W Moore, J Org Chem., 59,3284-3288 (1994) 219 Y Masaki, K Hashimoto, Y Serizawa, and K Kaji, Chem Lett., 18791880 (1982) Y Masaki, K Hashimoto, Y Serizawa, and K Kaji, Bull Chem SOC.Jpn., 57,3476-3482 (1984) 220 F Bohlmann and L Fiedler, Chem Ber., 114,227-231 (1981) 221 R K Dieter and J W Dieter, J Chem Soc., Chem Commun., 1378-1380 (1983) R K Dieter, Y J Lin, and J W Dieter, J Org Chem., 49, 31833195 (1984) 222 V Roussis and T D Hubert, Liebigs Ann Chem., 539-541 (1992) 223 S P Tanis and D B Head, Tetrahedron Lett., 23,5509-5512 (1982) 224 Volume of this series, p 84 225 M D Taylor, G Minaskanian, K N Winzenberg, P Santone, and A B Smith, 111, J Org Chem., 47,3960-3964 (1982) M D Taylor and A B Smith, 111, Tetrahedron Lett., 24,1867-1870 (1983) 226 S J Danishefsky and N Mantlo, J Am Chem Soc., 110,8129-8133 (1988) 227 E J Corey and J P Dittami, J Am Chem Soc., 107,256-257 (1985) 228 T Hirukawa, M Oguchi, N Yoshikawa, and T Kato, Chem Lett., 23432344 (1992) 229 T Honda and H Ishige, J Chem SOC.Perkin Trans 1,3567-3570 (1994) T Honda, H Ishige, M Tsubuki, K Naito, and Y Suzuki, J Chem SOC Perkin Trans 1,954-955 (1991) T Kametani, T Honda, H Ishizone, K Kanada, K Naito, and Y Suzuki, J Chem SOC.Chem Commun., 646-647 (1989) 230 P Weyerstahl, H Marschall-Weyerstahl, J Penninger, and L Walther, Tetrahedron, 43,5287-5298 (1987) 231 G S R Subba Rao and H Ramanathan, Indian J Chem., 20B, 1089 (1981) H Ramanathan and G S R Subba Rao, Indian J Chem., 30B, 90110 (1991) 160 A Sesquidecade of Sesquiterpenes 232 M Kato, A Ouchi, and A Yoshikoshi, Chem Lett., 1511-154 (1983) M Kato, A Ouchi, and A Yoshikoshi, Chem Lett., 1697-1700 (1984) 233 T.-L Ho and T W Hall, Chem Znd., 566 (1983) 234 S V Trivedi and V R Mamdapur, Indian J Chem., 25B, 1160 (1986) 235 T.-L Ho, Syn Commun., 11,605-607 (1981) 236 S V Trivedi and V R Mamdapur, Indian J Chem., 29B, 876-8 (1990) 237 W Oppolzer, P H Briner, and R L Snowden, Helv Chim Acta, 63,9679 (1980) 238 T.-L Ho and T W Hall, Syn Commun., 11,371-4 (1981) 239 M Nishizawa, H Takenaka, and Y Hayashi, Tetrahedron Lett., 25,43740 (1984) 240 B Maurer, A Hauser, and G Ohloff, Helv Chem Actu, 69,2026-37 (1986) 241 P Weyerstahl, C Christiansen, and H Marschall, Liebigs Ann Chem., 1325-8 (1992) 242 B M Trost and L T Phan, Tetrahedron Lett., 34,4735-8 (1993) The Total Synthesis of Natural Products, Volume10 Edited by David Goldsmith Copyright © 1997 by John Wiley & Sons, Inc Indices Indices Skeleton Index Acy clics farnesane p 1-12, 14-24 sesquilavandane P non-lsoprenold p 13 solanane P nor-sesquiterpene p 13 arternane p 23 non-isoprenoid p 25 Monocyclics bisabolane p 29-77, 96-97 elernane p 77-09 cyclocitral p 97-107 secoeudesrnane secoeudesrnane secoeudesmane secoeudesrnane secoeudesrnane p 108-110 p 110-112 p 113 p 1'13 p 145 gerrnacrane p 114-128 bicyclogerrnacrane p 116 hurnulane p 129-132 bicyclohurnulane p 132-133 4444 secocadinane secocadinane secocadinane secocadinane p 141 p 147 p 149 p 91-96 161 162 A Sesquidecade of Sesquiterpenes Monocyclics (continued) cyclofarnesyl p 138 cyclofarnesyl p 138-140 cyclofarnesyl p 138-140 >** secoguiane p 143-144 secoguiane p, 150 secoerimophilane p 136-137 nonisoprenoid p 134-136, 146 nonisoprenoid p 145 secoarornadendrane p 140 secohirnachalane p 146 lactarane secodrimane (secovellerane) p 140 p 148 nonisoprenoid p 142 non-isoprenoid (cyclocitral-related) p 147 nonisoprenoid p 144 The Total Synthesis of Natural Products, Volume10 Edited by David Goldsmith Copyright © 1997 by John Wiley & Sons, Inc Indices Author Index Acton 93 Adams 10 Akita 40 Anand 19,44 Asakawa 113 Asaoka 30 Avery 92 Baeckstrom Baker 50,69, 101 Baldwin 46, 82 Ban 89 Baptistella 51 Bari 50 Bartlett 22 Basavaiah 38 Bashkir Bergstrom 135 Bhat Biernacki 12 Bloch Bohlmann 18,43, 87-88, 136-139 Bornowski 24 Brinkman 66 Burke 75 Butsugan 14 Caballero 52 Cahiez 53 Caine 108 Cane Carpita 48 Chou Collum 1, 72 Conia 37 Corey 49, 131, 142 Craveiro 66 Danishefsky 141 De Clercq 126 de Groot 116,131 Delmond 55 Depezay 36 Dieter 139 Eicher 102 Findlay 109 Frdter 54 Fuji 59 Fujii 64 Fujisawa 4, 82 Fukumoto 22,54,103 Gosselin 106 Grieco 89 Grimm 44 Gros 10 Hagiwara 135 Hall 1, 57 Hauptmann 128 Haynes 94 Hirota 118 Ho 31,32,48,83, 146, 147 Hofheinz Honan 125 Honda23, 144 Hoye 105 Hudlicky 20 Ichikawa 5 Jacobi 69 Jefford 17, 20 Joseph-Nathan 39 Julia Kad 32 Kakisawa Kametani 1,99 Kato 84, 99, 143 Kid0 83 Kim 80,82 Kinghorn Kitagawa 119 Kitahara 127 Knight 19 Kodama 132, 133 Kraus 15 Krishna Rao 40 Kurihara 38 Kurth 104 Kutney 81 163 164 A Sesquidecade of Sesquiterpenes Kuwajima 60 Ravindranathan 58,94 Lansbury 95 Rossi 48 Lanzetta 17 Roth 93 Lee 8,39 Rouessac 106 Li 117 Rousseau 25, 34,55 Liu 95 Roussis 140 Magnus 124 SaB 41 Maldonado 58,64,83, 136 Sakurai 46 Mamdapur 146, 147 SBnchez 39,41 Mane 40,42,43 Sat0 8,9 Marco 113 Schlessinger 113 Marshall 123 Schreiber 115, 126 Martin 77 Schultz 64 Martin 52,57 Seoane 86 Masaki 138 Shibasaki 90 Masamune 104 Shirahama 132 Masson 33 Smith 68, 76, 141 Matsuda 33 Srikrishna 15 Maurer 149 Still 122 McMuny 79, 115,129 Strunz 35 Mehta Subba Rao 145 Miles 66 Sugimura 21 Moore 42, 137 Suginome 3, 130 Morgan SzBntay Morgans 63 Takahashi 117-121, 130, 133 Mori 12,60,65,98,102, 127, 128 Takano 30,32,36,37 Motoyoshiya 34 Takeda 35 Muckensturm 59 Takeshita 98 Nagano 65 Tanaka 107 Narasaka 70 Tanis 140 Negishi 3,5, 14 Tius 103 Nicolaou Tokoroyama 65 Nishizawa 148 Trost 78, 152 Nokami 17 Vig 85 Ohloff 100 Wakamatsu 80,88, 112 Olofson 62 Warren 46 Ono 40 Wender 124 Oppolzer 147 Weyerstahl29,53, 144, 149 Otera 16 White 106 Paquette 57, 101 Wijnberg 116 Pedro 86 Williams 3, 74 Prestwich 105 Wolinsky 58,63 Quintard 34 w u 93 Rao 35,43 Xu 96,97 Raucher 120 Yamamoto 11,47 Indices Yamashita 13, 107 Yoshikoshi 68, 83, 110, 134, 145 Zhou 91 165 The Total Synthesis of Natural Products, Volume10 Edited by David Goldsmith Copyright © 1997 by John Wiley & Sons, Inc 166 A Sesquidecade of Sesquiterpenes Subject Index acetylide 1, 11,23, 59, 100, 108, 109, 143, 150 acoragermacrone 117 acrylonitrile aldol condensation 9,21, 60, 75, 100, 105, 109, 110, 116, 125, 135, 138, 139,143 allene 114 allofarnesene ally1 imidate Claisen reaction 56 allylic chromium reagent 119 allylic halogenation 59 allylic oxidation 6, 7, 9, 150 allylic sulfoxide rearrangement 68 n-ally1nickel complex American cockroach 125 aminobisabolenes 55 ancistrofuran 101, 102 Andrographis 67 anionic oxy-Cope rearrangement 114, 121, 127 m-anisic acid 67 m-anisic ester 135 antineoplastic, antitumor 71, 104 ants 1, 14 aplysistatin 105-107 aristolactone 123 aromadendrene 131 arsonium ylide 96 arteannuin 90 Artemesia 22 artemether 92 artemisin 85, 113 artemisinic acid 92, 93 artemisinin 90-95 artemone 23 asymmetric hydrogenation athanasin 24 ar-atlantone 35 a-atlantanone 55 P-atlantanone 55 aza-Claisen reaction 103 Baeyer-Villiger oxidation 11, 64, 65,67, 121 baker's yeast reduction 65, 101 Bamford-Stevens reaction 138 Barbier reaction 33 Bayliss-Hillman reaction 38 Beckman reaction 148 beefsteak plant 13 benzenesulfenate benzenesulfinyl chloride benzyltrieth y lammonium permanganate 43 bergamot oil 54 bicyclogermacrene 115 bicyclohumulenone 132, 133 bilobanone 6458 binaphthol47 biomimetic 93, 106, 131, 132 bisabolangelone 59 a-bisabolene 46-48 P-bisabolene 46-48 y-bisabolene 49 y-bisabolene-8,9-oxide 52 bisabol- lO-ene-3,7-0xide 52 "bisabolene oxide" 53 8-epi-P-bisabolol 54 a-bisabolol46,53, 54 bisnorvernolepin 89 borane-dimethylsulfide BrCl56 bromination 99, 110, 142 bromoacetaldehyde 15 2-bromo-2-butene 3-bromobutenolide 14 bromogeraniol 19 3-(bromomethy1)furan 137 6-bromo-2-methylhept-2-ene 32 p-bromotoluene 34 but-1-en-3-yne butyllithium m-CPBA 10 cabreuva oil 148 cabreuva oxides 149 callitrin 87 caparappi oxide 99 carboalumination carbon disulfide 139 2-carene 79, 141 2-carone 108, 115 Carroll reaction 47 carvone 59,96, 109 carvone epoxide 143 catecholborane cerium chloride 100 chelotropic elimination Chinese orange oil chiral amide base 123 chloroacetone 136 chloromethylcarbene 37 3-chloromethylfuran 17 3-chlorophenol 135 chokol C 150 chromium carbonyl-naphthalene 10 cinammoyl72 cine substitution 79 citronellol 139 Claisen rearrangement 1, 15, 101, 119, 129, 146 cobalt-catalyzed coupling Compositae 87 conjugate addition 4, 30, 34,48, 81, 83,96, 109, 141, 142 Cope rearrangement 115,119 copper iodide , 14 costunolide 119 Costus oil 13 cottonseed oil 52 coumarin 148 p-cresol 146 m-cresol40 (croty1)ethoxydimethylsilane 65 cuprate 83 curcudiol40 curcuhydroquinone 39-40,44 curcumanolide A 143-144 Indices 167 a-curcumene 30, 32, 37, 38 ar-curcumene 1,32 curcupheno140 curcuquinone 39,40 curzurenone 84 [2 + 21 cycloaddition 115 cyclohexadiene monoepoxide 83 cyclohexenol83 cyclohexenone 63,82 cyclopentadiene cyclopropylcarbinyl ring opening 80 dactyloxene-B and -C 100-101 Danishefsky's diene 57 davanone 22-23 11,12-dehydro-8-deoxymelitensin 85 dehydrolasiosperman 17 dehydromelitensin 85 dehydromyodesmone 139 dehydromyomontanone 139 dehydromyopyrone 18 5,8-dehydro-4-oxonerolidol7 dehydroselenation 68 dehydrosulfenylation dendrolasin 1, 14-17 deoxymelitensin 85 deoxytrisporone 98 8-desoxy-isocaespito157 desoxysericealactone 88 di-tert-butyl squarate 42 diazotization 136 DIBAL 13, 16,18, 19,21, 109 dichloroketene 79, 111, 115 Dieckmann cyclization 84 Diels-Alder reaction 6,46,47,57, 70,73, 89,94, 126 diethoxyethylene 67 diethy laluminum tetramethylpiperidide 63 dihydroartemisinic acid 93,94 dihydrocarrisone 80 dihydrocarvone 119 dihydrocostunolide 119, 120 168 A Sesquidecade of Sesquiterpenes 4,5-dihydro-~-curcumen-4,5-diol 53 dihydrolimonene 126 dihydropyridine 64 dihydroxytiglate 122 diimide 142 diisopropyl tartrate 54 diketene dilithioacetate 70, 109, 110 dimethylacetamide 149 dimethylacrylonitrile 56 dimethylallyl alcohol 47 dimethylallyl phenyl sulfone dimethylallyllithium 23 dimethylcopperlithium 1,72, 108, 115, 123 dimethylcyclohexanedione 11 6,1O-dimethyl-9-methylene-undec5-en-2-one 13 dimethylhydrazone 13 dimethylsquarate 42 dimethylsuccinic ester 35 dimethylsulfonium methylide 126 dipolar cycloaddition 75 dissolving metal reduction 52, 53, 72, 1009 dithiane 72 electrochemical oxidation 139 electrocyclic reaction 40, 41, 114, 137 elemanolide 86, 87 a-elemene 80 p-elemene 78 y-elemene 79 p-elemenone 82, 83 p-elemol 80, 81, 109 elvirol 43 ene reaction 74,96 epicurzurenone 84 epiipomeamarone epoxidation 11, 110 epoxide deoxygenation 119 epoxy-a-bisabolene 50, 51 epoxyfarnesoate epoxysuccinate 72 eriolangin 110 eriolanin 111, 112 esterase 24 (ethoxy)lithium aluminum hydride 38 ethyl 2-bromocrotonate 20 ethyl bromoacetate 121 ethyl crotonate ethyl vinyl ether 15 ethylene oxide 14 ethynylation 149 eucalyptus oil 131 eucannabinolide 122 Eumorphia 138 farnesal 103 a-farnesene 2, P-farnesene farnesic acids farnesol4, farnesyl acetate 56, 118 Favorskii reaction 34, 79, 115, 143 fir trees 62 Firmenich 33, 100, 148 fluoride 10, 15, 84,90 formaldehyde 5,58 3-formyl-(2,6,6-trimethyl-2cyclohexenyl)-3-pentenal98 free-radical addition 21 free-radical deoxygenation 75 freelingnite 17 Fremy's salt 41 Friedel-Crafts 43, 129 furoixiolal44 furoventalene 134-136 3-furfural20, 139 2-furyllithum 19 3-furyllithium 18, 21, 24, 101, 138 3-furylmethanol 17, 19 (3-fury1)methyl Grignard 14 geijerone 78 geminal reductive acylation 60 geranial geranyl acetate 118 geranyl bromide 1, 2, , 7, 13, 15, 149 geranyl chloride 2, 107 geranyl phenyl ether 17 geranylacetic acid 106 geranylacetone9, 10, 11, 16, 115 germacrene-D 115, 126 germacrone 118 Givaudan 54 glutaric anhydride 40 glyceraldehyde acetonide 134 Greek tobacco 98 Grignard 5, 8, 11, 14, 30,97, 135, 145 Grob fragmentation 98, 125 guaiol 116 haageanolide 120 Hagemann's ester halolactonization 52 hanegokedial 141 Heck reaction 32, 34, 89 hedycaryol 116 hellianuol A 44 Henry reaction 58 heptelidic Acid 141 hernandulcin 60, 61 himachalenes 146 himasecolone 146 homogeranic acid 101 homogeranonitrile 104 homogeranyl Wittig reagent 107 homogeranyl alcohol 14 homogeranyl Grignard homoprenyl Grignard 11 , 61 homoprenyl iodide 24 homoprenyl phenyl sulfone 50 Horner-Wadsworth-Emmons reaction 10, 11,49, 131, 144, 146 Hosomi-Sakurai reaction 65 humulene 129-131 humulene oxide 132 humulenedione 131 Hunsdiecker reaction 52 Indices 169 hydroboration 3, , 8, 71, 72, 90, 95, 102, 130, 143 hydroformylation 73 hydrogenolysis 44,95 12-hydroxy-y-bisabolene50 P-hydroxyisobutyric acid 72 4,5-cis-3P-hydroxygermacranolides 121 hydroxyisogermafurenolide 88 2-hydroxymethyl-4-phenylthio- 1butene 15 12-hydroxypalisadin B 107 hydroxylate 109, 119, 127 hydrozirconation 48 igalan 87 insect juvenile hormone 62 iodocyclization 23-24 ipomeamarone 20-22 Ireland ester enolate Claisen 15, 92 isabelin 124 isobicyclogermacrenal 116 isobisabolene 46 isobutenyllithium 18 isocanambrin 146 iso-a-curcumene isofuranogermacrene 88 isogermafurenolide 88 isohumbertiol 149 isoledene 131 isoperezone 41,42 isoprene 47, 129 isoprene oxide isoprenyl phenyl sulfoxide isopropenyl Grignard 15 isopropenylbromide isopropylidenation , 15 4-isopropylcyclohexenone 114 isopulegol90 isovaleraldehyde 59, 62 Jones oxidation 8, 23, 144 Julia olefination 11, 50, 56 Julia rearrangement juvabiol62 170 A Sesquidecade of Sesquiterpenes ar-juvabione 43 melitensin 85 erythro-juvabione 64 p-menthene threo-juvabione 63 trans-menthenediol 148 juvabione 63-66 menthol 58 juvenile hormone 9-12 mercuric salts 106, 148 [Z14C]-juvenile hormone I11 10 metal-halogen exchange 136 methoxycyclopropyl cuprate 63 karatavic acid 148 methyl acorate 145 KHMDS 121 methyl crotonate 145 kinetic protonation 37 methyl cyclopropyl ketone 2, 11 kinetic resolution 10, 54, 79, 90, methyl dihydroarteannuinate 98,100 methyl Grignard 6, 11, 13,42 Knovenagel condensation 16 methyl isopropyl ketone 118 Kochi oxidative decarboxylation methyl nidorellaurinate 146 68,728 4-methyl-3-furylcerium 137 4-methyl-4-hexenal 22 lactaral 140 4-methyl-2-lithiofuran 19 lance0159 0-methylperezone 41 lead tetraacetate 109 methyl perillate 67 lepidozene 115 P-methyl-0-propiolactone Lewis acid 7, 10,47,72,74, 83, methyl senecioate 10 103, 131, 136,147 methyl tiglate 84 limonene 47,54, 148 methylalumination 2, 14 limonene bis-epoxide 60 3-methyl-3-butene- 1-01 limonene oxide , 1,62 methylcerium 150 linalool6, 100 3-methylcyclopentanone 139 linderalactone 124 methylenation 13 lithio-tert-butyl acetate a-methylenation 124 2-lithiofuran 139 a-methylenebutyrolactone 17 2-lithio-4-methyl-5methylenetriphenylphosphorane trimethylsilylfuran 24 107 lithiopropyne 42 methylheptenone 2, 39,60 lithium 17 methylheptenone epoxide 10 lithium aluminum hydride 83, 109 methylheptenyl acetate 146 methylsulfinyl chloride lithium amide 127 lithium dichlorocuprate 3-methyl-3-sulfolene lithium diisopropenylcuprate 84 3-methyl-5-(2,3,6liverwort 112 trimethylpheny1)-1-penten-3-01 147 methylvinylketone 90, 91 Michael addition 11, 18, 102, 110, malaria 90 malate 105 113, 145 microbial reduction 11 manganese carbonyl66 Mukaiyama aldol reaction 141 manganese oxidation 47, 146 McMuny titaniumcarbonyl myodesmone 139 myomontanone 139, 140 coupling 78, 115, 118, 129 myoporonelmyopyrone 18, 138, 139 myrcene 1, 8, 137 neolinderalactone 124 nerolidol6,99 neryl chloride Nezara viridula 50 ngaione 20-22 nickel carbony18 nickel-catalyzed coupling 135, 142 nitrile oxide cycloaddition 61 I-nitro- I-phenylthiopropene 84 nitropropene 84 nopinone 47,83 nuciferal31-32, 37-39 nuciferol 31-32, 36-38 5-octynoic acid 75 Oppenauer oxidation 146 organocuprate 54, 100 organomanganese 53 orthoester Claisen 31, 148 ovalicin 142 oxalyl chloride 43 oxazole [4 + 21 cycloaddition 68 oxidative decarboxylation 135 oxidative elimination 113 oxido-ylide 37 oxymercuration 1, 63 ozonolysis , 18, 23, 50, 51, 74, 85,92,96 palisadin A 107 palladium-catalyzed carbonylation 123 palladium-catalyzed coupling 2-4, 10,14, 150 palladium-catalyzed reductive cycloisomerization 76, 149 pallescensin 103 paniculide A, B, C 67-70 parvifoline 39 penlanpallescensin 104 pentadienyllithium 147 Indices 171 peracid oxidation 70 perezone 41-42 perillal67, 71, 146 perillyl alcohol periodate 142 periplanone 114 periplanone A 128 periplanone B 126-128 periplanone J 128 Peterson reaction phenyl vinyl sulfone 57 (phenylsulfiny1)acetonitrile 15 phenylselenide 60 ant pheromone 3,50 photochemical reaction 13, 67, 80, 98,114, 123 photoisabelin 123 photooxidation 1,7, 8,92, 148 phyllanthocin 71-77 phyllanthocindiol72 phytuberin 108-110 pinacol rearrangement 100 pinene 95 pleraplysillin-1 138 pleraplysillin-2 19 potassium tert-butoxide 23 prehnitene 147 prenyl Grignard 7, 60 propenyl cuprate 137 2-propenyllithium 42 protiodesilylation 142 pseudoionone Pummerer reaction 15,44, 126 pyridinium dichromate pyrolysis 6, 16,20, 109, 124, 131 qinghaosu 90-95 radical cyclization 15 Raney nickel 62 reductive 1,2-rearrangement 23 reductive alkylation 41 reductive halogenation 123 Reformatsky reaction 42 resolution 30, 72, 100 A Sesquidecade of Sesquiterpenes retro-ene reaction 131 Stryker's reagent 150 rhodiumisomerization, of sulfolene vinylepoxides 33 sulfonium ylide 72, 83 ricciocarpin A 102, 103 sulfoxonium ylide 132 Ritter reaction 56 Suzuki coupling 3, 8, 130 ruthenium tetroxide 92, 131 sydonic acid 43 172 Sandmeyer reaction 136 seco-drimane 148 seco-furanoeremophilane 136-137 secocrispiolide 145 selenation 68, 86, 110, 113, 126 selenonium 99 selenoxide elimination senecioyl chloride 54, 129 sericenine 125 sesquichamaenol 147 sesquilavandulol7 sesquiphellandrene 57 sesquirosefuran 14 Shapiro reaction 92 Sharpless directed epoxidation 15, 70,142 Sharpless asymmetric epoxidation 22, 31, 51, 54, 73, 96 shyobunone 84 sigmatropic rearrangement 78, 104, 118, 123 [2,3]-sigmatropic rearrangement 16,83 silver-catalyzed 18, 19, 143 Simmons-Smith reaction 21 a-sinensal , P-sinensal8,9, 16 singlet oxygenation 90-91,93-96 siphonidictidine 19 snyderols 104 sodium borohydride/nickel chloride 68 sodium iodide 34 sodium isopropoxide solanone , solvolysis 24, 37, 80 S American Myrocarpus wood 148 Southern green stink bug 50 tartrate 107 temisin 85 a-terpineol 80 terrestrol5 tetrabutylammonium oxalate 120 theonellin 56 theonellin isocyanide 56 thermolysis 2, 4,9 thujone 80 tiglaldehyde 13 tiglic acid 17 ar-todomatuic acid 43 tolaldehyde 34 tolhydroquinone 40 toluenesulfinate 137 tolyl cuprate 34 tolyl Grignard 32 tolylacetonitrile 37 Torreya nucifera 36 tosyl chloride tosyl hydrazone trialkylaluminum tridensone 113 triethylsilane 97 triflation 115 (trimethylsily1)isoprene 46 (trimethylsilylmethyl)methylether 90 trimethylsilyl triflate 22, 92 2,5,9-trimethyl-2-vinyl-deca-4,8- dienal 13 tropical green algae 98 ar-turmerone 30, 32-35 umbellifolide 113 umbelliprenin 148 vernolepin 88-89, 111 vernomenin 88 vinyl cuprate 1, 82 vinyl ether Claisen vinyl Grignard 114, 147-149 vinyl tin 10 vinyl lithium 2, 137 Wacker oxidation 147 Wittig 2, 3,47, 107, 138, 141 [2,3]-Wittig rearrangement 66, 118, 121,122 Wolff rearrangement 84 Indices wood termite pheromone 48 xanthorrhizol42 yingzhaosu A 90,96 yingzhaosu C 90,97 zedoary 84, 143 zempoalins 86 zerumbone 132 zinc 59, 63 zingiberene 58 zingiberenol 57 173 .. .THE TOTAL SYNTHESIS OF NATURAL PRODUCTS Edited by David Goldsmith Department of Chemistry Emory University Atlanta, Georgia THE TOTAL SYNTHESIS OF NATURAL PRODUCTS Volume 10 A Sesquidecade... (methylphenyl) tetrapropylammonium perruthenate toluenesulfonic acid THE TOTAL SYNTHESIS OF NATURAL PRODUCTS The Total Synthesis of Natural Products, Volume1 0 Edited by David Goldsmith Copyright... definition of a total synthesis If another sesquiterpene is the starting material, a change of the carbon skeleton must occur for the synthesis to qualify for inclusion It has been interesting to see the