THE TOTAL SYNTHESIS OF NATURAL PRODUCTS Edited by David Goldsmith Department of Chemistry Emory University Atlanta, Georgia THE TOTAL SYNTHESIS OF NATURAL PRODUCTS Volume 11 A Sesquidecade of Sesquiterpenes: Total Synthesis, 1980-1994 Part B: Bicyclic and Tricyclic Sesquiterpenes Michael C Pirrung, Andrew T Morehead, Jr., and Bruce G Young Department of Chemistry Duke University Durham, North Carolina A Wiley-Interscience Publication JOHN WILEY & SONS, INC New York Chichester Weinheim Brisbane Singapore Toronto This book is printed on acid-free paper @ Copyright 2000 by John Wiley & Sons, Inc All rights reserved 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, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4744 Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-mail PERMREQ @ WILEY.COM For ordering and customer service, call 1-800-CALL-WILEY Library of Congress Cataloging-in-PublicationData: CIP data available ISBN 0-471-18874-3 10 CONTENTS Acknowledgments Reagent Glossary 111 BICYCLIC SESQUITERPENES Introduction A Eudesmanes P-Eudesmol, a-Eudesmol, Intermediol, Neointermediol, Amiteol, Cycloeudesmol, Maaliol, aSelinene, P-Selinene, y-Selinene, Selinadiene, AE 1, Vetiselinene P-Dictyopterol, Selin-4(15)-ene-l~,ll-diol,Balanitol, Occidentalol, Isochamaecynone, Chamaecynone, Emmotin-G, Occidol Amitermes Defensive Substance, Isocelorbicol a-Cyperone, p-Cyperone, Carissone Eudesma-4( 14),7(11)-diene-8-one,Arctiol, P-Costol, P-Costal, Isocostic Acid, 3-Oxoisocostic Acid, 1Oxocostic Acid a-Costal, 7-Hydroxycostol, 7-Hydroxycostal 3-Oxoeudesmatrienoic Acid, 12,15-Dioxaselina-4,11diene Junenol, Acolamone Atractylon, Lindestrene, Tubipofuran 10 Glutinosone 11 Dehydroasterolide, Dihydrocallitrisin, Isoalantolactone, Septuplinolide, Ivalin, Oxodiplophyllin, Yomogin 12 Frullanolide, Tuberiferin, Deoxybrachylaenolide, Gazanolide, Arbusculin D, 3-0x0-11-hydroxyeudesmadienolide, Magnolialide, Maritimin, Dihydrosantamarine, asantonin xi xiii xv 1 10 14 15 17 20 21 22 23 25 25 29 V vi Contents B Cadinanes Calamenene Hydroxycalamenenes Methoxycalamenenes Mansonones, Perezinone 7,8-Dihydroxy.ll,12.dehydrocalamenene,Heritol Lacinilene C a-Cadinene, y2-Cadinene, e-Cadinene, e-Muurolene, 0-Cadinene, GCadinene Zonarene, Dihydropernetic Acid B, Veticadinol, Torreyol, Isocalamenediol, Cubenol, Epicubenol 1,4.Epoxycadinane, Verboccidentafuran, Hibiscone, Arteannuin B Halipanicine, Sclerosporin, Sclerosporal, Khusilal C Drimanes Bicyclofarnesic Acid, Drimenol, Albicanyl Acetate, Albicanol, Farnesiferol A Euryfuran, Valdiviolide, Confertifolin, Isodrimenin, Cinnamolide, Polygodial, Drimenin Fragrolide, Cinnamodial, Warburganal, Isotadeonal, Muzigidial, Colorata-4(13),8-dienolide,3pAcetoxydrimenin, Pereniporin A, Pereniporin B Driman-8,11-diol, Drim-9(1l)-en-8.01, 7-Oxo-llnordrimen-8-en-12-oic Acid, 1,1,5,6Tetramethyltetralin D Eremophilanes Nootkatone, Valencene, Isovalencenic Acid, Isovalencenol, Eremoligenol, Eremophilene, Valerianol, Eremophilone, Dehydrofukinone, Aristolone, Isopetasol, Petasol, Petasitolone Phomenone, Eremofortin B, Sporogen-A0 Ligularenolide, Ligularone, Petasalbine, Eremophilenolide, Furanoeremophilone, Furanoeremophilan-14,6a-olide E Miscellaneous Hydronaphthalenes Acetyldehydrorishitinol, Cinalbicol, 4Methoxyisocadalene, 4-Hydroxyisocadalene, 1Hydroxyisocadal-4-one, 2-Methoxy-7-norcalamenene, Maturone, Platyphyllide Ambrox, Pallescensin A Furodysin, Furodysinin Lemnal-Sa-en-2-0ne, Kanshone A, Nardosinone 33 33 38 39 41 42 46 50 52 54 54 57 62 68 70 70 75 77 79 79 83 87 88 Contents Valerane Valeranone Cryptofauronol Fauronyl Acetate Isoacanthodoral Nanaiomoal Thujopsene F Fused Ring Compounds: 6.3 Sirenin Sesquicarene Isosesquicarene G Fused Ring Compounds: 6.5 Pterosins Pacifigorgiol Tamariscol Brasilenol Conocephalenol Axamide-1 Axisonitrile-1 Axamide-4 Axisonitrile-4 Axisothiocyanate-4 Oppositol Pinguisone Deoxopinguisone Alliacolide Chiloscyphone Coriamyrtin Asteromurin Picrotoxinin Picrotin Oplopanone Anhydrooplopanone 10 Bakkenolide A Homogynolide A Homogynolide B Palmosalide C 11 Thapsane 12 Valerenal 13 8-Deoxyanisatin Anisatin Neoanisatin Noranisatin 14 Isovelleral Stearoylvelutinal 15 Marmalerin H Fused Ring Compounds: 6.7 ar-Himachalene a-Himachalene P-Himachalene yHimachalene Perforenone Guadalupol Epiguadalupol Perforene Widdrol Pallescensin E Pallescensin F Pallescensin G I Fused Ring Compounds: 6.8 Neolemnane Neolemnanyl Acetate Parvifolin J Fused Ring Compounds: 5.7 Lettucenin A 0-Bulnesene a-Bulnesol Gnididione Curcumenol Curcumol Liguloxide Kessane Alismol Guaianolides: Compressanolide Estafiatin Guaianolides: Arborescin 3-Epizaluzanin C Zaluzanin C Mokko Lactone Dehydrocostus Lactone Eremanthin vii 91 94 96 97 97 101 101 103 104 105 107 109 111 112 116 117 121 121 123 125 125 126 126 129 130 131 132 132 134 134 135 137 138 139 140 141 142 Guaianolides: Grosshemin Oxoisodehydroleucodin Jalcagauianolide 10 Pseudoguaianolides: Ambrosanolides-Confertin Rudmollin 11 Pseudoguaianolides: Helananolides- Aromatin Aromaticin Graveolide Fastigilin C Carpesiolin 12 Daucene Aspterric Acid 13 Mintsulfide Aphanamol.1 2-0xoisodauc-5-en-12-al 14 Furanol Furanether A Furanether B Furandiol Lactarorufin A Furoscrobiculin B 15 African01 16 Spathulenol Alloaromadendrane.4a.lOa.diol Cyclocolorenone Didehydroaromadendrane 17 Clavukerin A Clavukerin C Clavularin A and B K Fused Ring Compounds: 5.8 Precapnelladiene Poitediol Dactylol Asteriscanolide L Fused Ring Compounds: 4.9 Isocaryophyllene Caryophyllene Punctaporonin B M Fused Ring Compounds: 5.5 Pentalenolactone E Pentalenolactone Pentalenolactone G Pentalenolactone H Pentalenolactone P N Isolated Rings Cuparene Herbertene Tochuinol a.Cuparenone P-Cuparenone Laurene Epilaurene Isolaurene Allolaurinterol Cyclolaurene Aplysin Filiformin Aplysinol Isoaplysin Trichodiene Bazzanene Trichodermol Verrucarol Calonectrin Anguidine 12.13.Epoxytrichothec.9.ene 15-Hydroxytrichothec9.12.diene 10 Neosporol Sporol 11 Dihydrofomannosin Acetate Fomannosin Spirocyclic Systems Acoradiene a.Acoradiene Acoratriene P.Acoreno1 P-Acoradiene Acorone Acorenone Acorenone B 145 147 152 155 157 159 161 163 165 168 168 171 172 174 174 175 177 177 178 182 186 186 191 199 202 204 207 214 217 220 222 224 225 225 229 Contents ix Hinesol Agarospirol a.Vetispirene P-Vetispirene P.Vetivone Anhydro-P-rotunol Solavetivone 15.nor.Solavetivone 3Hydroxysolavetivone Aglycone A3 Lubimin Oxylubimin Isolubimin Lubiminol Vitrenal Spirolaurenone Erythrodiene Cinera.5.7.11.trien 9.one 10 a.Chamigrene P.Chamigrene Bromomethylenechamigrenone P Bridged Systems P.Santalo1 P.Santalene epi.P.Santalene a.Santalo1 a-Sant alene a.cis.Bergamotene P.cis.Bergamotene p-transBergamotene (E)-endo-a-Bergamoten-l2-oic acid (E)-endo-/3-Bergamoten-12-oic acid Pinthunamide Helminthosporal Upial Nakafuran.8 Nakafuran.9 Dihydropallescensin Dihydrospiniferin.1 Spiniferin-1 234 239 IV TRICYCLIC SESQUITERPENES A Angular Triquinanes Isocomene Silphinene 8-0x0-silphinene Pentalenene Pentalenic Acid Silphiperfolenes Methyl Cantabrenonate Subergorgic Acid B Propellanes Modhephene C Linear Triquinanes Hirsutene Capnellenes Coriolin Hypnophilin Hirsutic Acid C Cerotopicanol D Miscellaneous Fused Tricyclic Sesquiterpenes P-Bourbonene Panasinsene Italicene Protoillud-6-ene 8-Hydroxy-protoillud-6-ene Illudol Punctatin A Ptaquilosin Illudin M Sterpuric Acid Sterpurene-3.12.14-triol Sterpurene 242 247 249 249 250 251 254 254 262 265 266 268 270 275 275 275 280 286 296 305 305 311 312 325 343 354 357 357 360 363 366 X Contents E Bridged Tricyclic Sesquiterpenes Khusimone Zizaene Zizanoic acid Prezizaene Prezizanol Jinkohol Patchouli alcohol Norpatchoulenol Seychellene Cycloseychellene Longifolene Culmorin Longiborneol Copacamphor Ylangocamphor Cyclosativene Sativene cisSativenedio1 Sinularene Acetoxysinularene Quadrone Cedrene Isocedrenes 8.14.Cedranoxide 8.14 Cedranediol Biotol Pipitzols a.Copaene fl.Copaene fl.Ylangene Lemnalol Longipinene 9-Isocyanopupukeanane Gymnomitrol 10 Secoishwaranol Ishwarane 11 Rhodolauradiol Khusiol References Epilogue Author Index Subject Index Skeleton Index 370 370 377 382 386 394 406 414 416 418 419 420 422 423 456 461 466 The Total Synthesis of Natural Products, Volume11 Edited by David Goldsmith Copyright © 2000 by John Wiley & Sons, Inc 466 A Sesquidecade of Sesquiterpenes Subject Index (1-trimethylsilyloxy)isoprene, 15 (a-naphthy1)ethylisocyanate, 368 (acetoxy)isoprene,216,217 (benzyl)hydroxylamine,420 (bromo)methally1 bromide, 404 (cyanomethyl)phosphonate, 406 (cyclopentadieny1)cobalt dicarbonyl, 363 (lithio) methylphosphonate,228, 407,416 (methoxy)bromocrotonate, 398 (methoxymethy1ene)triphenylphosp horane, 120 (p-benzyloxy)acetophenone,229 (phenylse1eno)propionicacid, 29 (phenylsulfinyl)acetonitrile, 97 (phenylsulfinyl)butenolide, 224 (pheny1thio)vinylmethyl ketone, 35 (thiophenyl)vinylsilane, 15 (toly1)acetic acid, 193 (trimethylsilyl) isoprene, 43 (trimethylsilyl) propargyl bromide, 362 1,1,5,6-tetramethyltetralin,69 1,2-dimethylcyclopentene,188 1,3-diyl (trimethylenemethane) trapping, 312,349,376 1,4-dimethylcyclohexene,209 1,4-dimethylcycohexadiene,2 10 1,Cepoxycadinane, 50 1,6-dimethylcyclohexene,117 1-hydroxyisocadal-4-one,8 1 -oxocostic acid, 20 1-oxodihydromagniolalide, 12,13-epoxytrichothec-9-ene, 220, 22 12,15-dioxaselina-4,11-diene, 22 12-nor-alliacolide,110 15-hydroxytrichothec-9,12-diene, 222 2,2-dimethyl-3(2H)-furanone,23 2,2-dimethylcyclohexadienone,41 2,3-dimethylcyclohexadiene,39 2,3-sigmatropic rearrangement, 97, 192,232,358 2,4,4,6tetrabromocyclohexadienone, 252 2,5-dimethylcyclohexanone,378, 380 2,5-dimethylcyclopentanone,205 2,6-dimethyl-4hydroxybenzaldehyde, 234 2,6-dimethylcyclohexanone,4 2,6-dimethylcyclohexenone,237 2-allyl-2-cyclopentenone,123 2-bromo-P-chamigrene, 252 2-diazopropane, 164 2-methoxy-7-norcalamenene, 2-methylcyclohexane-1,3-dione, 20 2-methylcyclohexanone, 358 2-methylcyclohexenone, 72 2-methylcyclopentane-1,3-dione, 343 2-methylcyclopentanone, 21 2-methylcyclopentenone, 105, 147, 214,318,322,328 2-methyltropone, 98 2-oxoisodauc-5-en-12-al, 158, 159 2-oxoseychellene, 382 3,3-dimethylcyclopentanone,224 3,3-dimethylglutarate,405 3,4-dimethylcyclohexenone,89 3,5-dimethylanisole, 242 3,5-dimethylphenol, 24 3-(hydroxymethyl)crotonate, 118 3-cyclohexenone, 100 3-epizaluzanin C, 143 3-ethoxycyclohexenone, 222 3-furfural, 154 3-hydroxysolavetivone, 246 3-methoxy-4-methylbenzoate, 40 3-methyl-2-butena1, 125 3-methyl-5-isopropylphenol, 250 3-methylcyclohexenone,2,25 1, 359 3-methylcyclopentenone,220 3-methylglutaric anhydride, 137 3-0x0- 1l-hydroxyeudesma1(2),7(1l)-dien-6,13-olide, 33 3-oxoeudesmatrienoicacid, 3-oxoisocostic acid, 19 3-oxosilphinene, 285,286 3P-acetoxydrimenin,67 4,4-dimethylcyclohexanone,161, 181 4,4-dimethylcyclohexenone,170, 188 4,4-dimethylcyclopentene,180, 318,320 4,4-dimethylcyclopentenone,181, 334,402 4-hydroxyisocadalene,8 4-isopropyl cyclohexenone, 53, 117 4-methoxyisocadalene, 4-methylcyclohexenone,44,5 1, 220 5,5-dimethylcyclopentenone,322 5hydroxycalamenene, 35 5-methyl-5-chlorocyclopentenone, 203 5-oxosilphiperfol-6-ene, 299 6-methylcyclohexenone,22 7,8-dihydroxy-l1,12dehydrocalamenene, 40 7-hydroxycalamenene,36 7-hydroxycostal, 7-0x0- 11-nordrimen-8-en-12-oic acid, 69 7aH-silphiperfol-5-ene, 297 7PH-silphiperfol-5-ene,297 8,14-cedranediol, 410 8,9-dehydroasterolide,26 8-deoxyanisatin, 123 8-epi-oplopanone, 116 8-hydroxycalamenenes,37 Indices 467 8-methoxycalamenene,37 9-hydroxy-P-iso-obtusene, 420 9-isocyanopupukeanane, 417,418 9-keto-a-agarofuran, 15 a-acoradiene, 227,228 a-bulnesol, 136 a-cadinene, 43 a-cedrene, 407,408 a-chamigrene, 25 a-cis-bergamotene, 262 a-copaene, 415 a-costal, 21 a-cuparenone, 191-198 a-curcumene, 336 a-cyperone, 16,21 a-eudesmol, 3,4, a-himachalene, 127, 128 a-ionone, 269 a-phenylbutyrate, 101 a-santalene, 262 a-santalol, 261 a-santonin, 142 a-selinene, 7, , a-vetispirene, 236-238 acetonedicarboxylate, 12, 10 acetoxysinularene,392 acetyldehydrorishitinol, 80 acolamone, 23 acoradiene, 226 acoratriene, 228 acorenone, 231-233 acorenone B, 231-233 acorone, 229,230 acrolein, 257, 327,377 acrylonitrile, 149 Adams' catalyst, 416 AE , africanol, 161, 162, 172, 173 africene, 161 agarospirol, 235,237 aglycone A3,247 albicanol, 57 albicanyl acetate, 56 468 A Sesquidecade of Sesquiterpenes aldol, 16,49,72,77,88,89,90,63, arene-olefin photocycloaddition, 104, 109, 111, 113, 116, 125, 151,275,282,297, 303, 312, 130, 137, 138, 139, 148, 158, 16,346,406 164, 165, 173, 197,218,226, aristolene, 91 232,238,253,267,284,288, aristolone, 73 299,303,321, 322, 327,333, aromadendrane, 163 344, 347,348,358, 360, 361, aromadendrene, 139 371,374,376,384, 392,395, aromaticin, 153 402,404 aromatin, 152 alismol, 140 arteannuin B, 52, 109 allene, 184,310,404 Aspergillus, 68,76, 156 alliacol-A, 110 aspterric acid, 157 alliacolide, 110 asteriscanolide, 174 alloaromadendrane-4a,10a-diol, asteromurin, 115 164 atractylon, 24 allokhusiol, 375 axamide-1, 106, 107 allolaurinterol,203 axamide-4, 106 allyl bromide, 370 axisonitrile-1, 106, 107 allyl silane, 9,71, 129, 130, 133, axisonitrile-4, 106 152,228,321,343 axisothiocyanate-4, 106 allylidenecyclopropane rearrangement, 136 P-acoradiene, 229 aluminum trichloride, 414 P-acorenol, 229,233 ambreinolide, 83, 84 P-bourbonene, 358 ambrox, 84 P-bulnesene, 135, 136, 140 aminoaziridine, 383 P-cadinene, 44 Amitermes defensive substance, 14 P-chamigrene, 252,253 anguidine, 219 P-cis-bergamotene,263 anhydro-P-rotunol,241 P-copaene, 15 anhydro-oplopanone, 117 p-costal, 19 anhydrolactororufin A, 159 p-costol, 19 anisatin, 124 P-cuparenone, 196-199 anti-infective, 39 P-cyperone, 17 anti-Markovnikoff, 107 P-dictyopterol, 11 antibiotic, 343, 363 P-eudesmol, antifeedant, 60 P-himachalene, 127, 128 antileukemic, 27 p-ionone, 251 antitumor, 343,363 p-isocomene, 277 aphanamol-I, 158, 159 P-muurolene, 45 aplysin, 204-207 P-panasinsene, 359 aplysinol, 205 P-pinene, 262 ar-himachalene, 126 P-santalene, 258-260 arborescin, 143 p-santalenone, 258 arbusculin D, 33 p-santalol, 255, 256,262 arctiol, 19 p-selinene, 7, P-trans-bergamotene,263 Indices P-vetispirene, 236 p-vetivone, 237,239-241 P-ylangene, 415 Baeyer-Villiger, 77, 130, 169, 173, 225,240,259,263,323,385,398 bakkenolide, 77, 118, 120 balanitol, 11 Bamford-Stevens, 9,48 Barbier reaction, 210 Barton deoxygenation, 15,25, 108, 139, 160, 315, 321, 328, 353, 354,376,385,400,402,421 bazzanene, 208 Beckman fragmentation, 209,23 1, 258 Beckman rearrangement, 331,371 benzenesulfenyl chloride, 368 benzenethiol, 346,408 benzoquinone, 169,259 benzyne, 38,359 bergamot oil, 262 Bertram-Walbaumreagent, 386 bicyclofarnesic acid, 55 bicyclogermacranedione,49 bicyclohumulenone, 161 BINAP, 340 biotol, 412 Birch reduction, 104,270, 360,416 bis(trimethylsily1oxy)cyclobutene, 155,293 bis-trimethylsilylacetylene, 326 Blanc reaction, 194 boron annulation, 149 boron txifluoride, 240,409, 414 bracken fern, 101, 364 brasilenol, 104 Bredereck's reagent, 66 bromohydrin, 114, 117 bromoisoprene, 408 bromomethylenechamigrenone, 253,254 Brook rearrangement, 18,73 Buchner reaction, 126, 150 Burgess' salt, 20, 30, 74 butadiene, 390 469 butynal, 136 byssinosis, 41 cadinenal, 47 calamenene, 34, 38 calomelanolactone, 103 calonectrin, 19 campholenic acid, 404 camphorsulfonic acid, 255 capnellene, 325-338 capnellene-3P,8/3,1Oa,14-tetrol, 340 capnellene-3P,8P,lOa-triol,339 capnellene-SP,lOa-diol, 339,341 carbonylation, 125, 179, 183, 184, 186 carcinogenic, 363 carene, 165,248, 334 carissone, 17 carpesiolin, 154 Carroll reaction, 121 carvacrol, I carvomenthone, 35 carvone, 6, 16,41, 66, 84, 103, 115, 119,220,266,323 caryophyllene, 176 Castro-Stephens reaction, 368, 369 catalpol, 351 cationic rearrangement, 157,279, 14 cedranoxide, 410 cedrol, 412 ceric ammonium nitrate, 41 chamaecynone, 12, 13 chamigrene, 129 chiloscyphone, 111, 112 chloroacetyl chloride, 108 chloroacrylonitrile,372 chloromethyl benzyl ether, 402 chromium tricarbonyl, 36, 39, 230 Chugaev reaction, 23, 265 cinera-5,7,1l-trien-9-one, 250 Cineraria, 250 cinnamodial, 62 cinnamolide, 60 470 A Sesquidecade of Sesquiterpenes Criegee rearrangement, 66, 119, cis-(4-chloro)crotyl alcohol, 15 166 citraconic anhydride, 388 CrOg*dimethylpyrazole,82 citronellal, 47 Claisen condensation, 156, 178, crotonic acid, 126,409 194,227,258,395,356,378,413 cryptofauronol, 94, 135 Claisen rearrangement, 5, 115, 120, Cu(acac)2, 187 121, 169, 188,202,208,210, cubenol, 49 215,217,222,251,289,299, culmorin, 127,386 312,347,395,402,409 cumyl hydroperoxide, 173 Claisen rearrangement, cuparene, 187-189 Eschenmoser, 148 cuprates Claisen rearrangement, Johnson butenyl cuprate, 286 orthoester, 139, 162, 173,248, butyl cuprate, 238 393,403 methallyl cuprate, 402 Claisen rearrangement, Ireland methyl cuprate, 50,53, 90, 109, ester enolate, 174,210,213,317, 119, 164, 165, 171, 191, 197, 398,410 239,251,270,305, 335, 355, clavukerin A, 166, 167 339,341, 351,359,376,385, clavukerin C, 166 411,413 clavulerins, 166 tolyl cuprate, 194 Clemmensen reduction, 126,250 vinyl cuprate, 341,400 colorata-4( 13),8-dienolide,66 curcumenol, 138 compressanolide, 141 curcumol, 138 confertifolin, 57,59 Curtius reaction, 105, 106, 218 confertin, 148-150 cyclocolorenone, 164 Conia carbenoid method, 161 cycloeudesmol, Conia carbomercuration, 249 cyclogeraniol, 121 conjugate addition, 19, 123,221, cycloheptatriene, 185 240,247,280,328 cyclohexenone, 78,175,398 conocephalenol, 105 cyclohexenone-3-carboxylate,19 Cook-Weiss reaction, 287,310 cyclolaurene, 203 copacamphor, 387 cyclopentadiene, 169,259,260, Cope elimination, 95,317,385, 261,349,376,389 391,393 cyclopentane-1,2-dione,310 Cope rearrangement, 374,393,401 cyclopentane-1,3-dione, 148,372, Cope-Claisen, 32 387 copper hydride, 346 cyclopentanone, 188 copper triflate, 358 cyclopentene-4-carboxylicacid, Corey-Fuchs 355 dibromomethylenation, 12 cyclopentenone, 110,330,358, Corey-Yamamoto (2)-trisubstituted 366,370 allylic alcohol synthesis, 257 cyclopropanation, 5,72,97, 121, coriamyrtin, 113, 114 125, 136, 145, 161, 163, 167, coriolin, 344-353 171, 181,202,234,249,252, coriolin B, 352 cotton, 41 289,319,343,354,383,389, 393,401,415,416 cyclopropene [2+2] cycloaddition, 320 cyclosativene, 388 cycloseychellene, 379, 38 cyclotene, 200,210 6-cadinene, 44 D-mannitol, 258 6-selinene, dactylol, 172, 173 damsinic acid, 150 Danishefsky's diene, 25,52,215 Darzens, 195 daucene, 155,156 DBU, 348 DDQ, 240,351 debromoaplysin,204,207 debromoaplysinol, 205 decarbonylation, 158 dehydrocostus lactone, 144, 145 dehydrofukinone, 70,73 dehydrolinalool, 139 dehydrozizaenes,376 deMayo reaction, 155, 158, 168, 170,200 dendrolasin, 83 dendrolasin oxide, 85 deoxybrachylaenolide,33 deoxynorpentalenolactoneH, 184 deoxypentalenic acid, 290 deoxypinguisone, 108 di-.n-methanerearrangement, 11 diazodimedone, 15 DIBAL-H, 28,60,364,401 dibromocyclopropanation, 103, 135,163 dichlorocyclopropanation, 180, 373,411 dichloroketene, 117, 175, 180, 196, 197,286,355 dichromate, 30 dicobalt octacarbonyl, 184, 356, 403 Indices 471 dicyclopentadiene, 344 didehydroaromadendrane, 165 Dieckmann condensation, 41,72, 137, 156, 195,212,296,376, 407,411 Diels-Alder, 2,3, 6,7,8, 16, 18, 19,25, 38,43,44,46,49,50, 52, 53, 58, 59, 61, 72,73, 74, 80, 82, 83,94,95, 99, 121, 127, 169, 185, 194, 196,209,210,215, 216,217,225,226,230,235, 242,245,250,255, 256,258, 260, 261,268,281,285, 307, 320,321,329, 331, 334, 362, 366,368,369,371,372,375, 377,378,380,382,384,385, 388,389,390, 391, 392,396, 397,400,408,411,416,418 diethoxyethylene, 224,330, 362 diethyl methylmalonate, 356 dihydro-P-ionone, 55 dihydrocallitrisin, 26, 78 dihydrocarvone, 16,92,247 dihydrocostunolide, 32 dihydrofomannosin acetate, 224 dihydromagniolalide, dihydroorcinol, 9,24 dihydropallescensin D, 269 dihydropernetic acid B, 47 dihydroreynosin, 20, 32 dihydrosantamarine, 1, 32 dihydrospiniferin-1,270 diketene, 92 dilithioacetate, 145, 154 dimedone, 160 dimethoxyphenol, 409 dimethoxytoluene, 413 dimethyl acetylenedicarboxylate, 411 dimethylcyclopentenecarboxylate, 315 dimethylcy clopropenecarboxylate, 285 dimethyldioxirane, dimethylfulvene, 385,411 472 A Sesquidecade of Sesquiterpenes dimethyltitanocene, 170 epoxide-to-carbonyl rearrangement, dipolar cycloaddition, 164 78,185,232,266,310,346,411 dissolving metal (Li / NH3) epoxygermacranolide,32 reduction, 19,30,38,71,85,88, epoxygermacrene-D, 11 121, 141, 158, 160, 171, 182, eremanthin, 144 186,203,208,211,227,229, eremofortin B, 76 234,238,254, 266, 267,271, eremoligenol, 72 eremophilene, 72 286,290,292,298, 332,339, eremophilone, 72 349,360,363,386,394,411 dithiane, 37,45, 147,224,249 erythrodiene, 250 divinylcyclopropane Erythropodium, 249 rearrangement, 373,393,401 Eschenmoser's salt, 22, 110, 183, DMF dineopentyl acetal, 217 344 drim-9(1l)-en-S-o1,68,69 estafiatin, 142, 145 driman-8,l 1-diol, 69 ethyl (a-bromo)crotonate, 265 drimenin, 60, 61 ethyl (geranyl)acetate, 175 drimenol, 55 ethyl acrylate, 332 ethyl bromoacetate, 396 ethyl cyanoacetate, 19 &-amorphene,44 &-cadinene,43-46,54 ethyl diazoacetate, 127, 166,401, 415 &-muurolene,43 ethyl isobutyrate, 362,403 elatol acetate, 420 electrochemical oxidation, 409 ethyl magnesium malonate, 22 ethyl vinyl ketone, 15, 16 electrocyclic ring opening, 270 electroreductive cyclization, 92, ethylene, 224,299,361, 367 eucalyptus oil, 6,49, 139 335,367,405 emmotin-G, 14 eudesma-4(14),7(1 l)-diene-s-one, 18 endo-a-bergamoten-12-oic acid, eudesmadienone, 22 264 eudesmol, 10,91 endo-P-bergamoten-12-oicacid, euryfuran, 57,58,59 264 Evans-Mislow sulfenate-sulfoxide ene reaction, 45,46,47, 125, 138, rearrangement, 220,305,368 152, 169,215,307,308, 321, evodone, 24 327,361,367,370,391 epi-P-santalene, 257,259,260 farnesic acid, 414 epi-p-santalol, 257 farnesiferol A, 56 epi-precapnelladiene, 169 farnesol, 55,56 epicubenol, 50 fastigilin C , 153 epiguadalupol, 129 fauronyl acetate, 94 epilaurene, 201,202 Favorskii, 97, 166,227,309 epoxidation, 10, 15, 19, 32, 49, 63, fenchone, 398 75, 89,90,98, 110, 113, 114, Fetizon's reagent, 350 117, 133, 141, 142, 145, 154, filiformin, 204,206,207 161, 171, 173, 215, 221,222, Fisher indole synthesis, 190 243, 247, 310, 314, 334, 345, Fleming-Tamao oxidation, 14 347,349,371,404,419 fomannosin, 225 formaldehyde, 47, 152, 179,246, 350,359,394 fragrolide, 62,68 Friedel-Crafts, 69, 102, 126, 131, 154,173,228,253,365 Fries rearrangement, 34 frullanolide, 29 fukinone, 73,76 furan ring transformation, 58,232 furandiol, 159 furanether A, 159 furanether B, 160 furanoeremophilan-14,6a-olide, 79 furanoeremophilone, 78 furanol, 159 furfural, 88 furodysin, 88 furodysinin, 88 furoic acid, 78 furoscrobiculin B, 161 y-bisabolene-8,9-oxide, 252 y-Himachalene, 127 fl-Cadinene, 43 fl-Muurolene, 45 gansongone, Gatterman-Koch reaction, 241 gazanolide, 33 geranylacetone, 97,263 germacrene D, 107, 116,157 glutamic acid, 218, 358 glutinosone, 25 glycol cleavage, 197 glyoxal, 135 gnididione, 137, 138 graveolide, 153 Grignard, 1, 2, 5, 8, 9, 28, 35,42, 44,48,74,90,93,96, 103, 112, 117, 119, 123, 132, 140, 144, 163, 171, 177, 196, 203,235, 240,278, 290, 296, 301,305, 327, 334,336, 361, 370, 387, 388,391,392 Indices 473 methyl, 206,220,235,239,240, 267,310,345,365,366,368,409 but-3-yn-1-yl, 308 tolyl, 200 vinyl, 184,268, 326, 394,416 propargyl, 362 prenyl, 262 isopropenyl, 113,266,418 1-butenyl, 307 Grob fragmentation, 135, 151, 155, 159, 166,208,267,303,372,389 grosshemin, 146 guadalupol, 129 gymnomitrane, 208 gymnomitrol, 419 Hagemann's ester, 120 halipanicine, 52 Hall reductive arylation, 276 haloetherification, 114-116, 157, 213 haloform reaction, 210, 267, 298 halolactonization, 29, 139, 148, 331,337 HBr, 261,386,420 Heck reaction, 132 Helichrysum, 359 helminthosporal, 265-267 helmiscapene, Henry reaction, 95,408 herbertene, 190, 191 heritol, 41 hetero-Diels-Alder, 45, 145, 252, 257 Heterotheca, 37, 80 hexafluoropropyldiethylamine, 338 hexynd-01, 18 HF, 413 HI, 337 hibiscone, high pressure, 242, 391 hinesol, 8, 234-237, 254 hirsutene, 12-324 hirsutic acid C, 355, 356 Hoffman elimination, 209 474 A Sesquidecade of Sesquiterpenes homo-1,5-hydrogen shift, 276 isolaurene, 200, 201 homoenolization, 17 isolubimin, 244 homogeranonitrile bromohydrin, isopetasol, 74 249 isophorone, 41 homogynolide A, 119 isopinocampheol, 204 homogynolide B, 119, 120 isoprene, 45,99,226,33 Horner-Wadsworth-Emmons, 30, isoprene epoxide, 261 40,53,72, 104, 125, 167,228, isopropylacetylene, 393 261,263,264,296, 329, 369, isopropylcyclohexanol, 249 373,388,403,406,407 isosesquicarene, 99, 100 humulene, 161, 172, 179,294, 314 isotadeonal, 63,64 humulene oxide, 161, 338 isothiocyanate, 53 hydroacylation, 192 isovalencenic acid, 72 hydroboration, 4, 6,41,62, 74, 91, isovalencenol, 72 115, 121, 152, 174, 179, 187, ivalin, 28 241,248,268,312,326,344, italicene 360 350,352,354,355,363, 364, 374,376,393, 395,396,406, jalcaguaianolide, 147 408,409 jinkoholI1, 376 hydrosilation, 49, 181 Jones oxidation, 15, 119,224, 321, hydroxycarvone, 15 335,396,401 hypnophilin, 350,351, 352 junenol, 23 illudin M, 366 illudol, 224, 362, 363 Ireland phosphoramidate reduction, 401 ishwarane, 419 iso-a-cedrene, 409 isoacanthodoral, 95, 127 isoalantolactone, 27 isoamylene, 196 isoaplysin, 205 isobutenyl acetate, 196 isobutylene, 175,285,398, 399 isocalamenediol, 48 isocaranone, 247 isocaryophyllene, 175, 176 isocelorbicol, 15 isochamaecynone, 12, 13 isocomene, 276-280 isocostic acid, 19 isocurcumenol, 138 isodrimenin, 56,58,62 isodrimeninol, 60 isoeugenol, 265 K/Al2O3,49 kanshone A, 90, 111 kessane, 140 ketene [2+2] cycloaddition, 166, 190,205,262,278,300 KH, 210,251,407 khusilal, 54 khusimone, 370,37 Knovenagel condensation, 21,217, 359 Krapcho decarboxylation, 9,47, 118,197,236,396,411 lacinilene C methyl ether, 42 lactarorufin A, 160 Laurencia, 199,204, 249,253 laurene, 200-202 LDA, 374 lead tetraacetate, 62 Lemieux-Johnson oxidation, 267, 349 lemnal-5a-en-2-one, 89 lemnalol, 15 Lepista, 69 lettucenin A, 134 levopimaric acid, 65 levulinic acid, 112 Lewis acid, 9, 16, 18, 39,45,47, 50,76,78,87,94,95,97, 126, 130, 133, 134, 154, 157, 172, 207,209,232,239,247,269, 286, 288,294,299, 305, 308, 337,341,371,421 LiC1,236 ligularenolide, 77 ligularone, 77 liguloxide, 139 LiH, 250 limonene, 6,356 lindestrene, 24 lipase, 153, 190, 196, 305 lithio tert-butyl acetate, 110, 145 lithium reagents butenyl lithium, 298 n-butyl lithium, 53 sec-butyl lithium, 322 dibromomethyl lithium, 253 dichloromethyl lithium, 54 isobutenyl lithum, 104 isopropenyl lithium, 416 isopropyl lithium, 155 methyl lithium, 27,30, 36,48, 66, 89, 109, 139, 160, 218,220, 226, 232,234,235,237,270, 293, 309,327, 348,355,358, 367, 371, 375, 376, 378, 382, 384,392,402,409,413 propynyl(methy1)lithium, 389 tolyl lithium, 196 (tributy1)tin lithium, 162 trimethylsilyl lithium, 339 tris(pheny1thio)methyllithium, 322 vinyl lithium, 9, 377 lithium (trimethylsilyl)acetylide, 318 lithium acetylide, 171, 41 Indices 475 lithium aluminum hydride, 139, 249,411 lithium di-tert-butylbiphenylide, 373 lithium perchlorate, 420 lithium tetrabromonickelate,252 lithium tetramethylpiperidide,350 liverwort, 247 longiborneol, 384 longifolene, 383-386 longipinenes, 416 lubimin, 244 lubiminol, 245 m-CPBA, 215 m-cresol, 203 maaliol, magniolalide, magnesium, anthracene-activated 361 maleic anhydride, 385 malonate, 19, 38, 234, 246, 333, 337 Mander's reagent, 25, 105, 118, 356 Mannich reaction, 84, 116 manool, 59, 68 mansonones, 39 marasmanes, 159 Marasmius, 109 maritimin, I marmalerin, 126 Martin's sulfurane, 10 maturone, 82 McMurry titanium reductive coupling, 167, 175, 188, 200, 237,25 1,332,372 menthone, 47 mesyl chloride, 241 metathesis, 169 methacrolein, 393 methallyl bromide, 365 methoxybutadiene,220 methyl (phenylthio)acetate,394 methyl a-bromoacrylate, 419 476 A Sesquidecade of Sesquiterpenes methyl acrylater 92,216,240,242, muzigidial, 64, 66 407 MVK, 73,187,309,380,384 methyl bromopropionate, 407 methyl butynoate, 255, 362 N-methylaniline, 332 methyl cantabradienate, 302 N-phenylselenophthalimide,3 15 methyl cantabrenonate, 302 NaBH4, 158 methyl coumalate, 220, 391 Nagata cyanide addition, 243 methyl epoxycantabronate,302 nakafuran, 269 methyl farnesate, 3, 228 nanaiomoal, 95,96 methyl isovalerate, 392 nanaiomool, 95 methyl methacrylate, 95, 252 nardosinone, 91 methyl perillate, 98 Nazarov cyclization, 209, 285, 294, methyl triflate, 369 15,326,329,407 methyl(chloro)ketene,206 NBS, 32 methylbenzylamine,252 Nef reaction, 407 methylcopper, 396 neoanisatin, 124 methylenation, 20 neointermedeol, methylheptenone, 406,408, 41 neolemnane, 133 methylmalonyl dichloride, 101 neolemnanyl acetate, 133 methyloctalone, 21, 64 neosporol, 223 methylphosphonate,309 nerylacetone, 263 methylzirconation, 18 nitrile oxide cycloaddition, 56, 86, Michael addition, 16, 22, 35, 38, 95 46, 54, 72, 76,92, 107, 112, 148, nitro-2-butene, 407 253,265,267,290,300,320, nitroethylene, 226,408 332, 335, 340, 370, 380,382, nitromethane, 85 395,407,420 nitrone cycloaddition, 3, 317,420 Michael-Michael-Claisen, 240 nitrosation, 373 microbial oxidation, 382 nootkatone, 9,70,71, 129 microbial culture, 17, 197 nopinone, 1,90 microwave heating, 385 noranisatin, 124 mintsulfide, 158 norbornanone, 240,259,371 Mitsunobu reaction, 76, 143, 202, norbornene, 257 364,374 Norrish Type I1 reaction, 59, 207, MnO2,341 231,363 norzizaenes, 376 modhephene, 279-3 11 Nozaki-Takai methylenation, 203 Moffatt oxidation, 109 mokko lactone, 144 o-methylanisole, 230 monocyclofarnesate,3,55 obtusol, 129 monocyclohomofarnesicacid, 83 occidentalol, 12, 13 morpholine, 395 occidol, 13, 80 Mosher ester, 113 onitin, 102 Mukaiyama aldol, 383 oplopanone, 117 Mukaiyama’s salt, 402 oppositol, 107 Mukaiyama-Michael addition, 154 mushroom, 159 Indices osmylation (dihydroxylation), 15, 32,41,63,116,123,219,224, 339,390,397 oxa-di-n-methane rearrangement, 98,186,307,418 oxidative decarboxylation, 18,26, 282,344,380 oxidopyrylium ion, 94,135 oxocostic acid, 30 oxodiplophyllin, 28 oxoisodehydroleucodin, 146 oxy-Cope rearrangement, 87,137, 163,171,418 oxylubimin, 244,246 oxymercuration, 179 ozonolysis, 66,93,104,11 1, 119, 125,147,184,321,326,331, 333,346,396,402,404 n-ally1 palladium, 167,177,246, 325,333,353 n-bromocamphor, 88,383 n-bromotricyclene, 261 p-cresol, 135,173 z-cyclization, 9,44,48, 11 1, 116, 242 p205,34 pacifigorgiol, 103 palladium acetate, 350,396 pallescensin A, 85-87 pallescensin E, 131 pallescensin F, 132 pallescensin G , 132 palmosalide C, 18 panasinsene, 359 pantolactone, 256 parvifolin, 133 patchouli alcohol, 377,378 patchouli oil, 377 Paterno-Buchi reaction, 280 Pauson-Khand reaction, 160,184, 289,291,312,347,356,403 PCC, 183,322 PCl5, 157 PDC, 331 477 pentalenane, 314 pentalenene, 287-296,318,402 pentalenic acid, 290-292,295 pentalenolactone, 183 pentalenolactoneE, 178-182 pentalenolactoneF, 179,180 pentalenolactone G , 183,184 pentalenolactoneH,183 pentalenolactone P, 185 pereniporin, 67,68 perezinone, 39 perezone, 39,413 perforene, 130,201 perforenone, 129 perillal, 7,98 perillol, 232 periodate, 20,361,380 peroxymolybdenum, 392 persulfate, 406 petasalbine, 77 petasitolone, 75 petasol, 74 Peterson olefination, 63,106,107, 136,382 phenoxy cation [4+2] cycloaddition, 284,293 phenyl vinyl sulfide, phenyl vinyl sulfone, 95 phenylalanine, 16 phenyldiazaphospholidine,252 phenylseleninic anhydride, 68 phomenone, 75 photochemical 1,3-acyl shift, 108 photochemical rearrangement, 98 photochemical [ 1,3]-acyl shift, 332 photochemical [2+2]cycloaddition, 20,51,128,135,155,158,168, 173,183,184,206,224,231, 227,282,299,302, 310,313, 318,320,330,331,358, 359, 361,366,367,372,398,399,404 photochemical-thermalmetathesis, 11,46,48,63, 141,286,295, 328 phytoalexin, 134 phytotoxicity, 60 478 A Sesquidecade of Sesquiterpenes picrotin, 115 quadrone, 394-405 picrotoxinin, 114, 115 quinine, 252 pinacol rearrangement, 6, 116, 130, 160, 171,207,235,269,332, radical additionkyclization, 198, 375,400,418,421 201,226,269, 280,283,298, pinguisone, 108, 109 308, 309,312, 317, 331, 351, Pinner reaction, 388 320,380,405,406,408,414 pinthunamide, 264 Ramberg-Backlund, 352 piperidinium acetate, 97 Raney nickel, 322, 408 piperitone, 155 Red-Al, 246 piperylene, 80 Reformatsky reaction, 41,290 pipitzols, 39,413,414 retro-[2+2] cycloaddition, 155 platyphyllide, 83 retro-aldol, 3,6, 168, 171, 181, poitediol, 172 228,231,263,337 polygodial, 60, 61, 64 retro-Claisen, 184 polyolefin cyclization, 85 retro-Diels-Alder, 190,411 potassium hexamethyldisilazide, retro-ene reaction, 49, 335 27 retro-Michael, 41 precapnelladiene, 169-171 rhodium acetate, 193, 233, 252 prenyl bromide, 141,374 rhodolauradiol, 42 prezizaene, 373-376,421 Rickborn reaction, 349 prezizanol, 373-376 Riemer-Tiemann reaction, 415 Prins reaction, 28,47, 139, 149, ring transfer, 160,212, 240,279,286,378,380 Ritter reaction, 256 propargyl alcohol, 120 Robinson annulation, 15, 16, 17, propargyl sulfonium salt, 24 21,44,66, 73, 76, 113, 123, 156, propargyl zinc, 223 195,218,219,271,299,373 propargylidene, 100 rose bengal, 59 propiolate, 121,225, 362 rudmollin, 151 propyne, 160 Rupe rearrangement, 326,411 protiodesilylation, 44 ruthenium tetroxide, 6, 110, 114, protoanemonin, 112 123,352,356,405,413 protoillud-6-ene, 361 protoillud-7-ene, 360 Sakurai reaction, 71,228,317 ptaquilosin, 101, 365 samarium diiodide, 268, 351 pterosin C , 101 SAMP hydrazone, 78 pterosin M, 102 sandalwood oil, 255,259 pterosin Z, 103 santonin, 12, 31, 33, 143, 146 pulegone, 123,227,296,373 sativene, 389, 390, 391 Pummerer reaction, 90, 189 sativenediol, 390 punctaporonin B, 177 sclerosporal, 53 punctatins, 177,364 sclerosporin, 53 Sclerotinia, 53 pyrolysis, 8,46,49,96, 136,237, secoishwaranol,420 276,290, 312,326, 328,335, selenium dioxide, 21,97,215, 367, 358,385,405 413,414 Indices selenosulfonation,320,366 selin-4(15)-ene-l~,ll-diol, 11 selina-3,7(1l)-diene, selinene, 10 senecioic acid, 370 senoxydene, 305 sensitizer, 59 septuplinolide, 27 sesquicarene, 99 seychellene, 378-381 Shapiro reaction, , 165, 170,338, 392,401,409 Sharpless directed epoxidation, 113 Sharpless asymmetric epoxidation, 69,95, 195,207 Sheradsky reaction, 205 silphinene, 281,282,283,284, 294 silphiperfol-5-ene-3-ol,301 silphiperfol-6-ene, 297-300 silver ion, 23 1,400 silyl acyloin, 238, 367 silyl peroxide, 130 Simmons-Smith, 1,96, 163,237, 270,308,328,354,407 singlet oxygen, 42,57,59, 166, 248,404 sinularene, 391-393 sirenin, 97,98 sodium naphthalenide, 163 sodium telluride, 25 solavetivone, 243,247 sonication, 130,210, 259 spathulenol, 163 spiniferin-1,271 spirolaurenone, 249 sporogen-A0 1,76 sporogenic, 68 stearoyl velutinal, 159 Stereum, 366 sterpurene, 368, 369 sterpurene-3,12,14-triol,367 sterpuric acid, 367 Stevens rearrangement, 187 Stiles' reagent, 123, 179 subergorgic acid, 303, 304 479 sulfenylation, 17 sulfonium ylide, 53,57, 116, 117, 125,135,187,266 superoxide, 344 Swern-Moffatt oxidation, 77, 82 tamariscol, 104 tartrate, 348 TASF, 365 Tebbe reagent, 169,329 telomerization, 390 terrecyclic acid, 395,399 tert-butoxide, 12, 241,418 tert-leucine, 27 tetrahydroeucarvone, 415 tetraphenylporphyrin, 59 thallium (111), 122 thapsane, 121 thioketal, 19,22, 155 thionyl chloride, 58,80, 253,413 thiopropionate ketene(silyl)acetal, 154 thujone, 9, 17 thujopsene, 96 Tieffeneau-Demjanov reaction, 269 tiglic acid, 391 tochuinyl acetate, 189 tolyl methyl ketone, 195 torreyol, 48 tosylhydrazine, 147 tin hydride, 139, 140, 198,201, 224,318,334,380,411,414,415 trichodermol, 214,221 trichodiene, 208-214, 222 triethylphosphonoacetate,55 triisobutylaluminum, 171 trimethylanisole, 268 trimethylcyclopentanone, 326 trimethylcyclopentenone, 183 trimethylphosphite, 358 trimethylsilyl triflate, 247, 161, 199 trimethylsilyl chloride, 388 trimethylsilyl cyanide, 157 trimethylsilyl iodide, 89, 171, 18, 332 480 A Sesquidecade of Sesquiterpenes triphenylphosphite ozonide, 245 388,389, 391, 392, 394,400, tropone, 144,145, 164,173,413 401,406,407,411 tuberiferin, Wittig-Horner, tubipofurans, 24, 82 Wittig rearrangement, 364 tutin, 115 Wolff rearrangement, 181,285, 290,315,334 upial, 267, 268 Wolff-Kishner, 5, 84, 263, 390,409 valdiviolide, 57 valencene, 1, 72 valerane, 91 valeranone, 92-94 valerenal, 122 valerianol, 72 valinol, 193 verboccidentafuran, verrucarol, 215-217 veticadinol, 47 vetiselinene, 10 vetiver oil, 370 Vilsmeier, 13 vinyl phosphonium salt, 182, 378 vinyl silane, 395 vinylcyclobutanol rearrangement, viny Icyclopropane rearrangement, 236,237,276,277,297,3 12 vitrenal, 248 von Braun reaction, 390 Wacker oxidation, 165, 212, 238, 322,347 Wagner-Meerwein rearrangement, 109,216,314,383 warburganal, 63-65 Wharton rearrangement, 21,89, 299,395 widdrol, 130, 131 Wieland-Miescher ketone, 56, 65, 74,85 Wittig, 2,4, 10, 19,45,71,94, 106, 112, 117, 121, 139, 163, 169, 175, 180,208,209, 218,224, 240, 254,256,257, 258,267, 270,277,290,306, 307, 318, 321, 326, 331, 337, 346, 349, 354, 358, 361, 362, 367, 374, xanthate, 6,23,201 yabujirami, 11 yeast, 76, 212, 219,263 yangocamphor, 387 yomogin, 28 zaluzanin C, 143 zirconocene, 129 zizaene, 372 zonarene, 46 [2+2+2]cycloaddition, 102 [4+4] cycloaddition, 174 [6+2] cycloaddition, 332 .. .THE TOTAL SYNTHESIS OF NATURAL PRODUCTS Edited by David Goldsmith Department of Chemistry Emory University Atlanta, Georgia THE TOTAL SYNTHESIS OF NATURAL PRODUCTS Volume 11 A Sesquidecade... Synthesis of Septuplinolide The Koga group at the University of Tokyo has synthesized the antileukemic ivalin in optically active form using asymmetric synthesis. 62 The conversion of 200 to the. .. discovered by the synthesis of the erroneous structure), but the size of the literature in which natural products were prepared necessitates limiting our scope If another sesquiterpene is the starting