Volume 5 the total synthesis of natural products

Total Synthesis Of Natural Products, Volume Edited by John Apsimon Copyright © 1983, by John Wiley & Sons, Inc THE TOTAL SYNTHESIS OF NATURAL PRODUCTS The Total Synthesis of Natural Products VOLUME Edited by John ApSimon Ottawa -Carleton Institute for Research and Graduate Studies in Chemistry and Department of Chemistry Carleton University, Ottawa A WILEY-INTERSCIENCE PUBLICATION JOHN WILEY & SONS New York Chichester Brisbane Toronto Singapore A NOTE TO THE READER This book has been electronically reproduced tiom digital information stored at John Wiley & Sons,Inc We are pleased that the use of this new technology will enable us to keep works of enduring scholarly value in print as long as there is a reasonable demand for them The content of this book is identical to previous printings Copyright 1983 by John Wiley & Sons, Inc 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 Libnwy of Congress Cataloging in Publication Data: ApSimon, John The total synthesis of natural products Includes bibliographical references Chemistry, OrganiGSynthesis I Title QD262.A68 547l.2 72-4075 ISBN 0-471-09808-6 (v ) Printed in the United States of America 10987654321 Contributors to Volume Samuel L Graham, Department of Chemistry, University of California, Berkeley Clayton H Heathcock, Department of Chemistry, University of California, Berkeley Michael C Pirmng, Department of Chemistry, University of California, Berkeley Frank Plavac, Department of Chemistry, University of California, Berkeley Charles T White, Department of Chemistry, University of California, Berkeley Preface The art and science of organic synthesis has come of age This is nowhere more apparent than in the synthetic efforts reported in the natural products area and summarized in the first four volumes of this series This present volume describes the synthetic activities reported for a 10-year period only in the sesquiterpene field-evidence enough for the successful efforts of the synthetic organic chemist in recent years Professor Clayton Heathcock and his colleagues have produced a masterly, timely and important contribution, the breadth of which necessitates a complete volume in the series The sixth volume in this series is in an advanced stage of preparation and will contain updating chapters on the subject matter included in the first two volumes together with a description of synthetic efforts in the macrolide field A seventh volume, covering diterpene synthesis, is in preparation JOHN APSIMON Ottawa, Canada October 1982 vii Contents The Total Synthesis of Sesquiterpenes, 1970- 1979 CLAYTON H HEATHCOCK SAMUEL L GRAHAM MICHAEL C PIRRUNG FRANKPLAVAC T WHITE CHARLES Index 543 ix Total Synthesis Of Natural Products, Volume Edited by John Apsimon Copyright © 1983, by John Wiley & Sons, Inc Total Synthesis of Sesquiterpenes, 1970-79 CLAYTON H HEATHCOCK, SAMUEL L GRAHAM, MICHAEL C PIRRUNG, FRANK PLAVAC, AND CHARLES T WHITE Department of Chemistry, UniversiQ of California, Berkeley, California Introduction Acyclic Sesquiterpenes A Farnesol and Farnesene B Terrestrol, Caparrapidiol, and Caparrapitriol C Juvenile Hormone D Sinensals E Fokienol, Oxonerolidol, and Oxodehydronerolidol F Gyrindal G Sesquirosefuran and Longifolin H Davanafurans I 6 11 17 22 24 25 21 Contents I Dendrolasin, Neotorreyol, Torreyal, Ipomeamarone, Freelingyne, and Dihydrofreelingyne Monocyclic Sesquiterpenes A acurcumene, Dehydro-a-curcumenes, Curcuphenol, Xanthorrihizol, Elvirol, Nuciferal, or-Turmerone, Curcumene Ether, and Sydowic Acid B Sesquichamaenol C Bisabolenes, Lanceol, and Alantone D a-Bisabolol, adisabololone, Deodarone, Juvabione, and Epijuvabione E Deoxytrisporone, Abscisic Acid, and Latia Luciferin F Caparrapi Oxide, 3P-Bromo-8-epicaparrapi Oxide, Ancistrofuran, Aplysistatin, and a- and @-Snyderols G Isocaespitol H Lactaral I y-Elemene, @-Elemenone,Shyobunone, and Isoshyobunone J Saussurea Lactone and Temsin K Vernolepin and Vernomenin L Pyroangolensolide and Fraxinellone M Ivangulin, Eriolanin, and Phytuberin N Hedycaryol, Preisocalamendiol, Acoragermacrone, Costunolide, Dihydrocostunolide, Dihydroisoaristolactone,and Periplanone-B Humulene Bicarbocyclic Sesquiterpenes; Hydronaphthalenes A Eudesmanes (1) Occidol, Emmotin H, Rishitinol, and Platphyllide (2) a-Cyperone, P-Cyperone, /I-Eudesmol, and 8-Selinene (3) Juneol, 10-Epijuneol, and 4-Epiaubergenone (4) Cuauhtemone (5) P-Agarofuran, Norketoagarofuran, and Evuncifer Ether (6) Rishitin and Glutinsone (7) Occidentalol (8) Santonin, Yomogin, Tuberiferine, Alantolactone, Isotelekin, Dihydrocallitrisin, and Frullanolide B Cadinanes (1) Aromatic Cadinanes (2) d a d i n e n e , yz-Cadinene, a-Amorphene, Zonarene, and Epizonarene (3) a-Cadinol and Torreyol C Drimanes (1) Driman-8-01, Driman-8,1l-diol, and Drim-8-en-7-one (2) Confertifolin, Isodrimenin, Cinnamolide, Drimenin, Futronolide, Polygodial, and Warburganal 28 35 35 46 47 55 68 75 81 84 84 90 93 107 109 114 122 124 124 124 129 134 136 137 140 143 149 157 157 161 166 169 169 170 Contents (3) Pallescensin A D Eremophilanes (1) Valencene, Nootkatone, 7-Epinootkatone, Isonootkatone, and Dihydronootkatone (2) Fukinone and Dehydrofukinone (3) Isopetasol, Epiisopetasol, and Warburgiadone (4) Eremophilone ( ) Furanoeremophilanes (6) Cacolol E Miscellaneous Hydronaphthalenes (1) Valeranone and Valerane (2) Khusitine and 8-Gorgonene F Hydronaphthalenes Containing an Additional Cyclopropane Ring Other Bicyclic Sesquiterpenes A Isolated Rings (1) Taylorine and Hypacrone (2) Cuparene, a-Cuparenone, and 8-Cuparenone (3) Laurene and Aplysin (4) Trichodiene, Norketotrichodiene, 12,13-Epoxytrichothec-9-ene, Trichodermin, and Trichodermol ( ) Debromolaurinterol Acetate B Bridged Systems (1 Camphorenone, Epicamphorenone, a-Santalene, a-Santalol, 8-Santalene, epi-@-Santalene,@-Santalol,and Sesquifenchene (2) a-bans-Bergamotene C Spirocyclic Systems (1) Spirovetivanes (2) Acoranes (3) Axisonitrile-3 (4) Chamigrenes D Fused Ring Compounds: 3,6 (1 Bicycloelemene (2) Sirenin and Sesquicarene E Fused Ring Compounds: 5,s (1 Pentalenolactone F Fused Ring Compounds: 5,6 (1) Hypolepins and Pterosin B (2) Bakkenolide A (3) Oplopanone (4) Picrotoxinin G Fused rings: 5,7 (1) Guaiazulenes: Bulnesol, a-Bulnesene, Guaiol, Dehydrokessane, and Kessanol 178 180 180 188 192 195 202 212 215 215 218 221 228 228 228 230 235 238 248 249 249 263 264 264 284 306 306 313 313 314 318 318 323 323 325 327 330 333 333 References 535 399 G.L Buchanan and G A R Young, J Chem SOC.,Perkin I, 2404 (1973); J Chem Soc., Chem Commun., 643 (1971) 400 N H Andersen and H S Uh, Tetrahedron Lett., 2079 (1973) 401 H -J Liu and S P Lee, Tetrahedron Lett., 3699 (1977) 402 N.H Andersen and F A Golec, Jr., Temhedron Lett., 3783 (1977) 403 J N Marx and S M McGaughey, Tetrahedron, 28, 3583 (1972) 404 See ref 2, pages 413-416 405 M.T Edgar, A E Greene, and P CrabbC, J Org Chem., 44, I59 (1979) 406 See ref 2, pages 417-423 407 D Caine and P F Ingwalson, J Org Chem., 37, 3751 (1972) 408 J A Marshall and J A Ruth, J Org Chem., 39, 1971 (1974) 409 See ref 2, Scheme 4, page 408 410 D Caine and J T.Gupton, J Org Chem., 40, 809 (1975) 411 J A Marshall and W R Snyder, J Org Chem., 40, 1656 (1975) 412 R A Kretchmer and W J Thompson, J Am Chem SOC.,98, 3379 (1976) 413 P DeClercq and M Vandewalle, J Org Chem., 42, 3447 (1977) 414 P Kok, P.DeClercq, and M Vandewalle, Bull Soc., Chem Belg., 87, 615 (1978) 415 P A Grieco, Y Ohfune, and G Majetich, J Am Chem SOC., 99, 7393 (1977) 416 (a) R Peel and J K Sutherland, J Chem SOC., Chem Commun., 151 (1974) (b) J S Bindra, A Grodski, T K Schaaf, and E J Corey, J Am Chem Soc 95, 7522 (1973) 417 P A Grieco, T Oguri, S Burke, E Rodriguez, G T DeTitta, and S Fortier, J Org Chem., 43, 4552 (1978) 418 (a) M.R Roberts and R H Schlessinger J Am Chem Soc., 101, 7626 (1979) (b) G Quallich and R H.Schlessinger, ibid., 101, 7627 (1979) 419 P T Lansbury and A K Serelis, Tetrahedron Lett., 1909 (1978) 420 P A Wender, M A Eissenstat, and M P Filosa, J Am Chem Soc., 101, 2196 (1979) 421 J A Marshall and R H Ellison, J Am Chem Soc., 98, 4312 (1976) 422 M F Semmelhack, A Yamashita, J C Tomesch, and K Hirotsu J Am Chern SOC.,100, 5565 (1978) 423 C H.Heathcock, E G Delmar, and S L Graham, J Am Chem Soc., 104, 1907 (1982) 424 M Demuynck, P DeClercq, and M Vandewalle, J Org Chem., 44, 4863 (1979) 425 c H Heathcock, T C Germroth and C M Tice J Am Chern SOC., 104, 0000 (1982) 536 References 426 (a) Y Ohfune, P A Grieco, C -L.Wang, G.Majetich, J Am Chem Soc., 100, 5946 (1978) (b) P A Grieco, Y Ohfune, and G Majetich, J Org Chem., 44, 3092 (1979) 427 P A Grieco, Y.Ohfune, and G Majetich Tetrahedron Leu., 3265 (1979) 428 P Kok, P DeClercq, and M Vandewalle, J Org Chem., 44, 4553 (1979) 429 (a) P T Lansbury and D Hangauer, Tetrahedron Leu., 3623 (1979) (b) P T Lansbury, D G.Hangauer, and J P Vacca, J Am Chem Soc., 102, 3964 (1980) 430 M Soucek, Coll Czech Chem Commun., 27, 2929 (1962) 431 M Yamasaki, J Chem SOC.,Chem Commun., 606 (1972) 432 (a) H deBroissia, J Levisalles, and H Rudler, J Chem Soc., Chem Commun., 855 (1972) (b) idem., Bull Soc Chim Fr., 4314 (1972) 433 (a) J Froborg, G Magnusson, and S ThorCn, J Org Chem., 40, 1595 (1975) (b) T Fex, J Froborg, G Magnusson, and S.ThorCn, ibid 41, 3518 (1976) (c) J Froborg and G.Magnuson, J Am Chem Soc., 100, 6728 (1978) 434 See ref 2, pages 396-402 435 E Wenkert and K Naemura, Synth Commun., 3, 45 (1973) 436 G.Mehta and S K Kapoor, J Org Chem., 39, 2618 (1974) 437 E Piers and E H.Ruediger, J Chem Soc., Chem Commun., 166 (1979) 438 A G GonzPlez, J Darias, J D Martin, and M A Meliln, Tetrahedron Lett., 481 (1978) 439 S Danishefsky and K Tsuzuki, J Am Chem Soc., 102, 6891 (1980) 440 See ref 2, Scheme 42, page 480 441 M Bertrand and J -L.Gras, Terrahedron 30, 793 (1974) 442 A Kumar, A Singh, and D Devaprabhakara, Tetrahedron Left., 2177 (1976) 443 A Kumar and D Devaprabhakara Synthesis 461 (1976) 444 E Piers, R W Britton, and W de Waal, Can J Chem., 49, 12, 1971 445 A Tanaka, R Tanaka, H Uda, and A Yoshikoshi, J Chem Soc., Perkin I, 1721 (1972) 446 S Torii and T Okamoto, Bull Chem SOC.Jupa4 49, 771 (1976) 447 See ref 2, Scheme 17, page 538 448 T Matsumoto, K Miyano, S Kagawa, S Yii, J Ogawa, and A Ichihara, TefrahedronLeft., 3521 (1971) 449 Y Ohfune, H Shirahama, and T Matsumoto, Tetrahedron Left., 4377 (1975) 450 H.Takeshita, H Iwabuchi, Kouno, M lino, and D Nomura, Chem Len., 649 (1 979) 451 D Helmlinger, P de Mayo, M Nye, L Westfelt, and R B Yeats, Tetrahedron Lett 349 (1970) References 537 452 S R Wilson and R B Turner, J Org Chem., 38, 2870 (1973) 453 W J Greenlee and R B Woodward, J Am Chem SOC.,98, 6075 (1976) 454 R K Boeckrnan, Jr and S S KO,J Am Chem SOC.,102, 7146 (1980) 455 (a) P T Lansbury, N Y Wang, and J E Rhodes, Tetrahedron Lett, 1829 (1971) (b) P T Lansbury and N Nazarenko, ibid., 1833 (1971) 456 P T Lansbury, N Y.Wang, and J E Rhodes, Tetrahedron Lett.;2053 (1972) 457 H Hashimoto, K Tsuzuki, F Sakan, H Shirahama, and T Matsurnoto, Tetrahedron Lett., 3745 (1 974) 458 F Sakan, H Hashimoto, A Ichihara, H Shirahama, and T Matsurnoto, Tetrahedron Lett., 3703 (1971) 459 B M Trost, C D Shuey, F DiNinno, Jr and S S McElvain, J Am Chem Soc., 101, 1284 (1979) 460 K Tatsuta, K Akimoto, and M Kinoshita, J Am Chem Soc., 101, 6116 (1979) 461 K Tatsuta, K Akimoto, and M Kinoshita, J Antibiot., 33, 100 (1980) 462 (a) S Danishefsky, R Zarnboni, M Kahn, and S J Etheredge, J Am Chem SOC.,102, 2097 (1980) (b) S Danishefsky and R Zamboni, Tefrahedron Lett., 3439 (1980) 463 M Shibasaki, K Iseki, and S Ikegami, Tetrahedron Leu., 3587 (1980) 464 A E Greene, Tetrahedron Left., 3059 (1980) 465 R D Little and G W Miller, J Am Chem SOC., 101, 7129 (1979) 466 W Oppolzer, K Battig, and T Hudlicky, Helu Chim Acta, 62, 1493 (1979) 467 M C Pirrung, J Am Chem SOC., 101, 7130 (1979); 103 82 (1981) 468 L A Paquette and Y K Han, J Org Chem., 44, 4014 (1979) 469 W G Dauben and D M Walker, J Org Chem., 46, 1103 (1981) 470 S Chatterjee, J Chem SOC.,Chem Commun., 620 (1979) 471 Ref 468, footnote 16 See also J Cornforth, Tetrahedron Lett., 709 (1980) 472 R M Coates, S K Shah, and (1979) 473 G Biichi and P R W Mason, J Am Chem SOC., 101, 6765 -S.Chu, J Am Chem SOC.,101, 6767 (1979) 474 S C Welch and S Chayabunjonglerd, J Am Chem SOC.,101, 6768 (1979) 475 Y.-K.Han and L A Paquette, J Org Chem., 44, 3731 (1979) 476 477 478 479 See ref 2, Scheme 11, pages 526-527 J E McMurry, J Org Chem., 36, 2826 (1971) See ref 2, page 523 (a) E Piers, R W Britton, R J Keziere, and R D Srnillie, Can J Chem., 49, 2620 (1971) (b) E Peirs, R W Britton, R J Keziere, and R D Smillie, ibid., 538 References 49, 2623 (1971) (c) E Piers, M B Geraghty, F Kido, and M Soucy, Synth Commun., 3, 39 (1973) (d) E Piers, M B Geraghty, and M Soucy, ibid., 3, 401 (1973) (e) E Piers, R W Britton, M B Geraghty, R J Keziere, and R D ) Peirs, R W Britton, M B Smillie, Can J Chem., 53, 2827 (1975) (IE Geraghty, R J Keziere, and F Kido, ibid., 53, 2838 (1975) (g) E Piers, M B Geraghty, R D Smillie, and M Soucy, ibid., 53, 2849 (1975) 480 (a) G L Hodgson, D F MacSweeney, and T Money, Tetrahedron Lett., 3683 (1972) (b) G L Hodgson, D F MacSweeney, and T Money, J Chem Soc., Perkin I, 2113 (1973) (c) C R Eck, G.L Hodgson, D F MacSweeney, R W Mills, and T Money, ibid., 1938 (1974) 481 S N Baldwin and J C Tomesch, Tetrahedron Lett., 1055 (1975) 482 P Bakuzis 0.S Campos, and M L F Bakuzis, J Org Chem., 41, 3261 (1976) 483 M Yanagiya, K Kaneko, T Kaji, and T Matsurnoto, Tetrahedron Leu., 1761 (1979) 484 (a) E Piers and H -P Isenring, Synth Commun., 6, 221 (1976) (b) E Piers and H -P Isenring, Can J Chern., 55, 1039 (1977) 485 J E McMurry and M G Silvestri, J Org Chem., 41, 3953 (1976) 486 P A Collins and D Wege, Ausi J Chem., 32, 1819 (1979) 487 See ref 2, Scheme 9, pages 518-519 488 J E McMurry and S J Isser, J Am Chem Soc., 94, 7132 (1972) 489 R A Volkmann, G C Andrews, and W A Johnson, J Am Chem Su 91, 4777 (1975) 490 W Oppolzer and T Godel, J Am Chem Soc., 100, 2583 (1978) 491 (a) S C Welch and R L Walters, Synth Comrnun., 3, 15 (1973) (b) S C Welch and R L Walters, ibid., 3, 419 (1973) (c) S C Welch and R L Walters, J Org Chem., 39, 2665 (1974) 492 See ref 2, pages 521-525 493 E J Corey and D S.Watt, J Am Chem Soc., 95, 2302 (1973) 494 (a) M Miyashita and A Yoshikoshi, Chem Commun., 1091 (1971) (b) M Miyashita and A Yoshikoshi, J Chem Soc., Chem Commun., 1173 (1972) (c) M Miyashita and A Yoshikoshi, J Am Chem Soc., 96, 1917 (1974) 495 See also C H Heathcock and R A Badger, Chem Commun., 1510 (1968) and C H Heathcock, R A Badger, and R A Starkey, Org Chem., 37, 231 (1972) 496 E J Corey, M Behforouz, and M Ishiguro, J Am Chem Soc., 101, 1608 ( 1979) 497 H.Yamamcito and H L Sham, J Am Chem Soc., 101, 1609 (1979) 498 E J Corey and M Ishiguro, Tetrahedron Lett, 2745 (1979) References 539 499 See ref 2, pages 492-503 500 E Piers, W de Waal and R W.Britton, J Am Chem Soc., 93, 5113 (1971) 501 (a) K J Schmalzl and R N Mirrington, Tetrahedron Lett., 3219 (1970) (b) R N Mirrington and K J Schmalzl, J Org Chem., 37, 2871 (1972) (c) R N Mirrington and K J Schmalzl, ibid., 37, 2877 (1972) 502 See ref 2, Scheme 2, pages 497-498 503 See ref 2, Scheme 3, pages 501-502 504 (a) N Fukamiya, M Kato, and A Yoshikoshi, Chem Commun., 1120 (1971) (b) N Fukamiya, M Kato and A Yoshikoshi, J Chem Soc Perkin /, 1843 (1973) 505 F Naf and G Ohloff, Helv Chim Act@ 57, 1868 (1974) 506 G Friter Helv Chim Acta, 57, 172 (1974) 507 M E Jung and C A McCombs, J Am Chem Soc., 100, 5207 (1978) 508 D Spitzner, Tetrahedron Lett., 3349 (1978) 509 K Yamada, Y Kyotani, S Manabe, and M Suzuki, Tetrahedron, 35, 293 (1979) 510 P Teisseire, P Pesnelle, B Corbies, M Plattier, and P Manpetit, Recherches, 19, 69 (1974) 511 W Oppolzer and R L Snowden, Tetrahedron Left., 3505 (1978) 512 J -L Gras, Terrahedron Lett., 4117 (1977) 513 F Kido, H Uda and A Yoshikoshi, J Chem SOC.,Perkin I, 1755 (1972) 514 D F MacSweeney and R Ramage, Tetrahedron, 27, 1481 (1971) 15 See ref 2, Scheme 8, pages 15-5 16 516 See ref 2, Scheme 10 pages 417-418 517 A Deljac, W.D MacKay, C S J Pan, K J Wiesner, and K Wiesner, Can J Chem., 50, 726 (1972) 518 R M.Coates and R L Sowerby, J Am Chem SOC., 94, 5386 (1972) 519 E Piers and J Banville, J Chem Soc., Chem Commun., 1138 (1979) 520 G Biichi, A Hauser and J Limacher, J Org Chem 42, 3323 (1977) 521 H -J Liu and W H Chan, Can J Chem., 57, 708 (1979) 522 P Naegeli and R Kaiser, Tetrahedron Lett., 2013 (1972) 523 E Corey and R D Balanson, Tetrahedron Lett., 3153 (1973) 524 See ref 2, Scheme 6, page 510 525 P T Lansbury, V R Haddon, and R C Stewart, J Am Chem ,Sot., 96, 896 (1974) 526 See also ref 2, Scheme and accompanying 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T Hayakawa, H Nakamura, K Aoki, M Suzuki, K Yamada, and Y Hirata, Tetrahedron, 27, 5157 (1971) (b) K Yamada, M.Suzuki, Y Hayakawa K Aoki, H Nakamura, H.Nagase, and Y Hirata, J Am Chem Soc., 94, 8278 (1972) (c) M.Suzuki, Y Hayakawa, K Aoki, H Nagase, H Nakamura, K Yamada, and Y Hirata, Tetrahedron Lett., 331 (1973) References 541 545 (a) Y Inubushi, T Kikuchi, T Ibuka, K Tanaka, I Saji, and K Tokane, J Chem SOL, Chem Commun., 1251 (1972) (b) Y Inubushi, T Kikuchi, T Ibuka, K.Tanaka, I Saji, and K Tokane, Chem Pharm Bull., 22, 349 (1974) 546 A S Kende, T J Bentley, R A Mader, and D Ridge, J Am Chem Soc., 96, 4332 (1974) 547 W R Roush, J Am Chem Soc., 100, 3599 (1978) 548 K Yamamoto, I Kawasaki, and T Kaneko, Tetrahedron Lefr., 4859 (1970) 549 D N Brattesani and C H Heathcock, J Org Chem., 40, 2165 (1975) 550 R F Borch, A J Evans, and J J Wade, J Am Chem Soc., 99, 1612 (1977) Total Synthesis Of Natural Products, Volume Edited by John Apsimon Copyright © 1983, by John Wiley & Sons, Inc Index Abscisic acid, 68, 69 Acetoacetic ester, dianion of, 8,69 a-Acetoxyacrylate, Diels Alder Addition of, I16 Acetoxy function reductive removal of, I Acetyl methanesulfonate, 485 Acetylmethylene triphenylphosphorane, reaction with citraconic anhydride,.33 Acoradiene, 291,379 P-Acoradiene, 285,294 y-Acoradiene, 285,292 8-Acoradiene, 285.292 Acoradiene, unnamed, 285 Acoragermacrone, I 14, I 17 Acoranes, 284 a-Acorenol 285.29 I P-Acorenol, 285.29 I 294 Acorenone, 285,294,300 Acorenone B, 285,294 Acorone, 285,292,300,302 Acyloin condensation, 284 Adams’ catalyst, 500 African army worm, 170 8-Agarofuran, 137 Agarospirol, 265,275,277.283 Alantolactone, 149, 152 Alantone, 53 a-Alantone, 47 a-Alaskene, 285 P-Alaskene, 285 Aldol condensation, 79, 121, 128, 168, 186, 268 crossed, 62 Alkylation with I-trimethylsilyl-3-bromoI-propyne, by Stork’s metalloenamine method, 300 Alkyl o-nitroselenoxide, 93 a-AUylnickel reagent from reaction of nickel carbonyl with prenyl bromide, 25 Aluminum amalgam, 480 Aluminum chloride, 179 Aluminum isopropoxide, 91, 324 Ambrosanolides, 347 Ambrosin, 347,355 American cockroach, 121 Amino nitrile from [2.3]-sigmatropic rearrangement of ammonium ylide, 18 a-Amorphene 161, 163 Ancistrofuran, 75 78 Ancistrotermes cavithorax, 78 Anhydro-P-rotundol, 265.277 Aplysin, 235,237 Aplysistatin 75 79 Aromatic cadinanes, 157 Aromaticin, 369, 375 Aromatin 376,396 Attractylon, 152 Axinella cannabina, 306 Axisonitrile, 306 Baeyer-Villiger oxidation, 69, 110, 355,426 Bakkenolide A, 325 Balsam 62 elam ford-Stevens reaction: deoxygenation by, 114, 135 variant of, 66 Barton reaction, modified, 140 Beckman fragmentation, 99 Beckman rearrangement, nitrone version, 356 Benzenesulfinate ion, elimination of, 68 Benzyl chloroformate, 449 a-trans-Bergamotene, 263 Bicarbocyclic sesquiterpenes, 124 Bicycloelemene, 313 Bicyclofarnesol 169 Bigelovin, 369,372 Bisabolane family 35 543 544 Index a-Bisabolene, 47 8-Bisabolene, 47,49 y-Bisabolenes, 47, 50 a-Bisabolol, 55 a-Bisabololone, 55,59 a-Bisabolols, radio-labeled, 59 Bischloromethyl furan, 381 Bisulfate ester, reduction of, Boron trifluoride, 179 Boron trifluoride etherate, 259 10-Bromo-a-chamigrene, 308.3 I 3/3-Bromo-9-epicaparrapioxide, 75, 77 (E)-o-Bromolongifolene, 385 N-Bromo succinamide, 81 cyclization with, 388 Bulgarian peppermint oil, 13 a-Bulnesene, 333,335 Bulnesol, 333 /-Butyl chromate, 71, 75 allylic oxidation with, 206,342 3-Butyn-2-01dilithium salt of, 184 Cacalol, 212 Cadalenes I57 Cadinanes, 157 y,-Cadinene, 16I , 163 E-Cadinene, 161 162 a-Cadinol, 166 Caespitol, 81 Calamenes, 157 Calcium in ammonia, 246 Camphorenone, 249,436 Caparrapidiol, 10 Caparrapi oxide, 75.76 Caparripitriol, 1 ( + )-Carone, 187 Carotol, 377, 379, 381 Carpesiolin, 369.375 Carroll reaction, 18 Carvone, 143,330,449 Castoramine, 500,505 Cecropia Cl,- and C,, juvenile hormones (JH) 11 Cedradiene, 484 a-Cedrene, 484,485,486 A’-Cedrene, 484 Cedrol, 484,485,487 a-Chamigrene, 306 Chinese orange oil, 17 Chloranil, 386 /runs-w-Chloroperillene, 30 Chromium trioxide, in acetic acid, 468 Chromous hydroxide, reduction by, 23 Chromyl chloride oxidation, 232 Cinnamolide, 170, 173 Cirrusjunos, 13 Claisen acylation 501 Claisen rearrangement, 15,21.50,213,241, 290,389,456,476 of eater enolate, 389 orthoacetate method, 16 stereorandom, 196 Cobaltous acetate, 81 Complicatic acid, 409 Confertifolin 170, 172 Confertin, 347,360 Copabomeol, 429,432 Copacamphene, 429,430,432,439 Copacamphor, 250.429,432,436 a-Copaene, 452 8-Copaene, 452 Copaisobomeol, 429,432 Cope elimination, of amine oxide, 104 Cope rearrangement, 18.88 Copper carbonate, 324 Coriolin, 405,412 Costunolide, 114, I18 Cram-Felkin model, for asymmetric induction, 28 Crandall-Rickborn isomerization, 20 Cu(acac), catalyzed rearrangement of diazoketone, 226 Cuauhtemone, 136 Cubebenes, 393 Cubebol, 393 Cuparene, 230 a-Cuparenone, 230.232 8-Cuparenone, 230,234 Curcumene, 44 a-Curcumene 35,36 Curcumene ether, 35.44 Curcuphenol, 35,42 Cyanide: conjugate addition of, 273 in dimethyl sulfoxide, 13 Cyclization, acid catalyzed, 30,68 12 + 2) cycloaddition of I - methylcyclohexanone and(s)-piperitone, T B Cyclocitral, 389 Cyclocolorenone 344 Cyclocopacamphene, 429 Cyclocopacamphor, 432 a.,9-Cycloeudesmol 221,224 /?,o-Cycloeudesmol, 22 I , 224 /3,/3-Cycloeudesmol,22 I Cyclopropyl carbinol solvolysis, 13 Cyclosativene, 429,436,437 Cycloylangocamphene, 429 a-Cyperone, 113, 129 /3-Cyperone, 129, I30 Damsin, 347,350,356 Damsinic acid, 347, 357 Darzens acylation, 320 Index Darrens condensation, 171 Daucene, 377,381 Daucol, 377,379.38 Davanafurans, 27 Davana oil, 27 DBP, 375.417 DDQ, 159,346 DDQ oxidation, 150 ( f)-Debromoaplysin, 238 ( f)-Debromolaurinterol acetate, 248 Dehydro-a-curcumene, 35,37 Dehydrofukinone, 188 9,IO-Dehydrofuranoeremophilane,202 Dehydrokessane, 333,339 Demjanov rearrangement, 487 Dendrobine, 510 Dendrobium nobile (Orchidacae), 10 Dendrolasin, 29 Deoxydamsin, 347 Deoxygenation Ireland’s method, 136 Deoxynupharamine, 500,509 Deoxynupharidine 500,502 Deoxytrisporone 68 DesoxynorpatehoulenoI, 47 Dibromocarbene, addition of, 495 I,l-Dibromo-2-ethoxycyclopropane, carbanion of, I Dibromomethyllithium, 186 Dichlorocarbene, under conditions of phase transfer, 22 I Dichloroketene, (2 + 21 cycloaddition of, 10 Dichloromaleic anhydride, 182 a,a-Dichloromethyl methyl ether 407 Didehalocaespitol, 83 Dieckmann cyclization, 218,277,427,438 Diels-Alder addition, of a-acetoxyacrylate, I16 Diels-Alder reaction, 95, 125, 126, 146, 162, 177, 184, 191, 194, 207,256,258,282, 283,294,320, 384,413,437,456,460, 466,470.481,516 with Danishefsky diene, 21 with ethyl acrylate, 218 intramolecular, 201,220,403,463,464, 466,487 inverse electron demand, 452 methyl vinyl ketone and isoprene, 56 a-Diethylphosphonopropionitrile,453 Dihydroarbiglovin, 341 Dihydrocallitrisin, 149, 153 Dihydrocarissone, 136 Dihydrocavone, 138,306,379,432 Dihydrocostunolide, 114 118 (3S)-2,3-DihydrofarnesoI(20), Dihydrofreelingyne, 28,34 Dihydro-P-ionone, 76, 171 177 Dihydroisoaristolactone, 114, I19 545 Dihydronootkatone, 180, 187 Dihydrosylvecarvone, 180 Diimide, 487 Diisobutylaluminum hydride, 252 Dilithio acetate, 95,371 Dilithioacetoacetate 99 Dimethyl diazomalonate, 497 Dimethyllithiomethylphosphonate,356 Dimsylsodium, 385,431,471 Disiamylborane, 296 Disodium tetracarbonylferrate, 400 Douglas fir, 62 Driman-8-01, 169 Driman-8,1 I-diol, 169 Drimanes, 169 Drimanic acid, I7 I (*)-Drimenin 170, 173 Drim-7-en-ll-ol, 169 Drim-8-en-7-one, 169 y-Elemene, 84 8-Elemenone, 84, 86 Elm wood, 157 Elvirol, 35,42 Emmons reaction, 72 Emmotin-H, 124, 126 Endoperoxide singlet oxygen oxidation of, 32 Ene reaction, intramolecular, 294 Enolate Claisen rearrangement, 155 Enolate ester Claisen rearrangement, 88 Enol phosphate, 69 ( *)-7,8-epialanolactone, 154 4-Epiaromadendrene, 344,346 4-Epiaubergenone, 134, 136 9-Epibicyclofarnesale, I75 7-Epibulnesol, 334 Epicamphorenone, 249 Epicarrisone, 145 2-Epi-a-cedrene, 487 8-Epidnmanic acid, 171 Epi-y-eudesmol, 139 Epieuryopsonol, 202,207 4-Epiglobulol, 344,346 7-Epiguaiol, 337 10-Epi-hinesol,275 10-Epihysterin, 366 Epiipomeamarone, 3-Epiisopetaso1, 192 10-Epijuneol, 134, 135 Epijuvabione, 55.62 7-Epinootkatone, 180, 199 3-Epinupharamine, 509 Epi-8-santalene, 249 6-Epishyobunone, 89 Epizizaene, 473,477 Epizizanoic acid, 473 546 Index Epizonarene, 161 164 12,13-Epoxytrichothec-9-ene, 238,240 Eremophilanes, 180 Eremophilenolide, 202,205 Eremophilone, 195 Eriolanin, 109, I12 Eschenmoser’s Mannich salt 97 Estafiatin, 34 I , 342 Ethoxyethynylmagnesium bromide, I08 -Ethoxy-2-methylbutadiene phosphonium salt from 40 Ethyldiazoacetate, 483 Ethyl-3-fury1 acetate, 31 Ethyllithium, 167 Ethyl malonyl chloride, 99 Ethyl thioethoxymethyl sulfoxide, 149 Eudesmanes, 124 Eudesmanolides, 149 8-Eudesmol, 129, 13 I Euryopsonol 202,207 Evuncifer ether 137, 139 Farnesal: acid catalyzed cyclization, 56 nitrone derived from, 59 8-Farnesene, (2E-60-Fameso1, 6, I16 (22-6E)-Farnesyl phosphate, cyclization of, 56 Favorskii rearrangement, 243 Fokienol 22 Fraxinellone, 107 Freelingyne 28 33 Friedel-Crafts cyclization, 171 Friedel-Crafts reaction: with 2-methoxy-4-methyl phenol 213 with y-valerolactone 212 Frullanolide, 149, 155 Fukinone 188 Furanoeremophilane, 202.205 3~-Furanoligularanol.202,209 Furanoligularone, 202 3-Furyllithium 78 108, 109 3-Furylmethylmagnesium chloride 178 Futronolide 170 I74 Geraniol, 24 Geranyl acetate, 123 Geranyl acetone, I Geranyl senecionate, 89 Globulol, 344 Glutinosone, 140 8-Gorgonene, IS, 220 Greek tobacco 169 Grignard reagent: from 2-bromo-1 -butene I5 from (E)-l-brorno-3-methyl-I -butene, 164 Grob fragmentation, 66, 85,275,448,455 Guaianolides, 341 Guaiazulenes, 333 Guaiol, 333,335 Gymnomitrol 424 Gyrindal, 24 Haller-Bauer fragmentation, 264 62-Hedycaryols, 114, I 17 Helenalin, 369,371,373 Helenolides, 347, 369 Helminthosporal 429,442 a-Himachalene, 384 8-Himachalene, 384,387 Hinesol, 265,269, 275 283 Hirsutene, 405,409.4 I7 Hirsutic acid, 405 Hirsutic acid C, 407 Homocitral, 78 Homogeranic acid, Homogeranyl tosylate, 79 Homer-Wadsworth-Ernmons olefination, 13 Humulene, 122 Hydronaphthalenes, 124 3~-Hydroxyfuranoeremophilane,202.209 Hydroxy sulphone alkylation of dianion of 68 Hymenin, 341,352,369 Hypacrone, 228 Hypolepin A, 323 Hypolepin B, 323 Hypolepin C, 323 Hypoleprs punctata 323 Hypolepis punetato Melt., 228 Hysterin, 347, 366 Illudinine, 498 Illudol, 394 Indian vetiver oil, 218 N-lodosuccinimide 32 a-lonone, 74 p-lonone, 71 8-lonone, acid obtained from, 70 Ipomeamarone 28.31.32 Ishwarane, 493 Ishwarone, 493,496 Isoacorone 285,293,300,302 Isobisabolene, 47,49 Isobutenyllithium, 53 Isocaespitol 81 Isocaryophyllene, 39 I Isocomene, 419 2-lsocyanopupukeanane, 455 9-lsocyanopupukeanane 455,456 lsodihydroagarofuran, I39 Isodrimenin, 170, 172, 176 7-lsohimachalol, 384 Index lsohirsutic acid, 405 Isokhusimone, 48 I, 487 Isoligularone, 202,2 I I Isolongifolene, 492 lsomarasmic acid, 398 Isonootkatone, 180, 184, 187 lsopetasol, 192 194 Isopiperitone, I17 Isoprene, trimerization of, Isopropenyllithium, 326 lsopropenylmagnesium bromide, conjugate addition of, 130, 220,269 lsopropylidene group, novel method for introducing, 87 Isopropylidenetriphenylphosphorane,26 I lsopropyl magnesium chloride, PhSCu catalyzed addition of, 456 Isoshyobunone, 84,90 Isotadeonal, 170 175 Isotelekin, 149, 153 Ivangulin, 109 C,,-JH, 12 C,,-JH from rrans-geranylacetone 14 C,,- and C,"-Jtl, synthesis of /I-oxidophosphonium ylide method, I2 C,,-JH, 12, 15, 16 Juneol, 134 Juvabione, 55.62 Kessanol 333,340 Ketene dithioacetal, isoprene equivalent, 53 Keto phosphonate dianion of, 38 K husimone, 473.480 Khusitene, 218 Knoevenagel condensation, 234 with di-t-butyl malonate, 101 Kolbe electrolysis, homogeranic acid, Lacinilene C methyl ether, 157, 161 Lactaral 84 Lanceol, 47, 53 Latia lucifenn, 68,69 Laurencia caespitosa, Lauremia pac$ca 31 I Laurene, 235 ( =k )-Laurinterol methyl ether 248 Lead tetraacetate: decarboxylation, I42 oxidation with, 108, 128 Lemieux-Johnson cleavage, 475 Lemieux-Johnson oxidation, 326 Ligularone, 202,207,2 I I Limonene 132 free radical addition of carbon tetrachloride, 53 547 metallation of, with n-butyllithium and tetramethyl-ethyl-enediamine, 52 Limonene epoxides, 61 Limonin, 107 Linalool oxides, 27 Linifolin A, 369,372 Lithiated a-alkoxy nitrile, Stork-Maldonado method, 63 I -Lithio-cyclopropyl phenyl sulfide, 273 2-Lithio- I ,3-dithiane, alkylation by neopentyl iodide, 33 Lithio-methyl trimethylsilyl acetate 359 Lithium acetylide, addition of, 332 Lithium aluminium hydride-aluminium chloride, hydrogenolysis with, 27 Lithium aluminium hydride-sodium methowide, 24 Lithium diisobutenylcuprate 15 Lithium dimethylcuprate, 21 I 275 displacement of bromide with, 23 I Lithium divinylcuprate, 101 195 480, 516 Lithium ethylamine, 116.306 Lithium fluoborate, 273 Lithium hexamethyldisilazide, 374, 427, 489 Lithium metal, 84 Lithium naphthalenide, reduction by, 135 Lithium perchlorate 199 Lithiurn 2,2,6,6-letramethylpiperidide (LTMP) 147 Lithium tri-I-butoxyaluminohydride I Lithium tri-sec-butylborohydride, I 14 Lithium triethylborohydride, 497 Longiborneol, 446,449 Longicarnphor, 446.449 Longicyclene, 446 449 Longifolene, 446 Longifolin, 25 a-Longipinene, 452 P-Longipinene, 452 Lucas reagent, 134 McMurray reaction 440 Magnesium methyl carbonate, 322 Mannich alkylation 166,242,243 Mansonone D, 157, 160 Mansonone G, 157, 160 Marasmic acid, 398 Mayurone 22 1,225 [MeCuBrJ-[Li(i-Bu,NH)?] , 27 I Mercuric oxide, as aldol catalyst, 32 Mercuric trifluoroacetate, 77 Methallylmagnesium bromide, 40 Methallytriphenylphosphoniumbromide, 218 Methallytriphenylphosphonium chloride, Wittig reagent from, 168 548 lodex Methoxymethylenetriphenylphosphorane, 440 Methylation, Greico’s procedure, 150 Methyl bicyclofarnesate, 174 Methyl-2-butynoate cuprate addition to 16 3-Methylcrotonic acid, alkylation of dianion of, Methyl cyclogeranate, 69 Methylenation, Mannich method, 153 Methylenetriphenylphosphorane 141, 142 Methyl famesate 8, 81, 134 Methyl Ruorosulfonate, 363 3-Methyl-2-furyllithium, 26 5-Methyl-2-furylIithium 27, 232 3-Methyl-2-furylmetallic reagent: bisfurylmercury 26 f‘urylmagnesium bromide, 26 Methyl geranate, 15 Methyl isopropenyl ether, 484 Methyl isozizanoate, 475 Methylmagnesium bromide, copper-catalyzed conjugate addition of, 339.373 Methyl o-nitrophenyl disulfide, 412 Methyl perrilate 65 2-Methyl- I -propenyllithium, 23 Methylsulfinyl carbanion, 494 Methyl trimethylsilyacetate, anion of, 375 Methyl zizanoate, 474 Mexicanin I, 369, 372 Mexican medicinal shrub, I36 Michael addition, 1’29, 193,240, 245,337, 510 acid catalyzed, 155 intramolecular 99 with unsaturated nitro compound, 212 Mislow/Evans rearrangement, of allylic sulfoxide, 101 MOO,, molybdenium pentoxide, 176 Monocarboxyclic sesquiterpenes, 35 Monocyclofamesic acid, 173 Mukiayama addition, of I-f-butoxy-I-I-butyldimethylsilyloxyethylene, 489 Myrcene, 20 singlet oxygen oxidation, 30 Nagata cyanation 513 Neoambrosin, 347 352 Neotorreyol, 28 Nerolidol, 22.80 acid catalyzed cyclization of, 56 (6E)-Nerolidyl phosphate, cyclization of, 56 Neryl senecionate 88 Ni (COD),, 363 Nickel boride catalyst, 256,261 Nickel carbonyl coupling, of bis-allylic bromide, 122 Nishimura’s catalyst, hydrogenation with, 456 o-Nitroselenoxide, elimination of, 121 Nootkatone, 180, 182, 186,269 Norketoagarofuran, 137, 138 Norketotrichodiene, 238,246 Norpatchoulenol, 469 Nuciferal, 35, 40 Nupharamine, 500,508,509 Nuphar spp., 500 Occidol, 124, 133 ( + )-Occindentalol, 143 Oplopanone, 327 Organozinc reagent, from I-methoxy2-butyne, 66 Oxidation: f-butyl chromate, I with lead tetraacetate, 128 Lemieux-Johnson method, 462 modified Polonovski method, 263 with selenium dioxide 126 singlet oxygen, 16, I50 van Tamelen’s method I16 Oxidative elimination of o-nitrophenylselenide 107 Oxocrinol, 25 9-0~0-5,8-dehydronerolidol,22, 23 9-Oxonerolidol, 22 Oxy-Cope rearrangement, 117, 121, 164 Palladium, on barium sulfate, 503 Pallescensin A, 178 Parthenin, 347,352,369 Patchouli alcohol, 335,460,464,469 Pentalenolactone, 18 4-Pentenylmagnesium bromide, 247 Perforenone, 388 Perillartine, 65 (-)-Perillic alcohol, 64 Penplanone-B, 114, 121 Peroxyformic acid, 138 Pefasilesjaponicus Max., 325 Phenylthiomethyllithium, 237 Phenyl thiophenylsulfonate, 415 Photocitral-A, 340 Photooxygenation, 70 Phytuberin, 109, I13 Picrotoxinin, 330 8-Pinene, 186, 199 (-)-Pipendine, I19 Pipendine enamine: alkylation of, 107 of isovaleraldehyde, 168 Platphyllide, 124, 128 Polygodial, 170, 173 Polyphosphoric acid, 338 Potassium fluoride, in methanol, 470 Potassium triethylmethoxide, 462 Index Potassium triphenylmethide, 462 Potato tubers, 269 Preisocalamendiol, 17.88, I14 Prevernolepin, 95 Prevemomenin, 95 Prevost hydroxylation, 13 Prins reaction, 15, 422 intramolecular, 266,340 Protected cyanohydrin, conjugate addition of, 234 Protoilludanols, 394 Protoilludenes, 394 Pseudoguaianolides, 369 Psilostachyin, 355 Psilostachyin C 347 Pteridium aquilinum var Latiusculum, 324 Rerosin E, 324 R-( +)-Pulegone, 293 Pummerer rearrangement, 375 Pyridinium bromide, 171 Pyroangolensolide, 107 Qrocumerenone, 157, 160 Pyrovellerolactone, 38 I 549 Reformatsky reaction, 34,206,299,430,470 Reverse Claisen reaction, 297 Rhodium chloride, 282 Rishitin, 140 Rishitinol, 124 Robinson annelation, 141, 180,301,328.389, 513 acid-catalyzed, 151 (+)-fl-RotunoI, I14 Ruthenium tetroxide, 516 Sharpless reagent, 320 Shimalite, solid phase, acidic, 440 Shotten-Baumann acylation, 503 Shyobunone, 84.87 Silver carbonate, on celite, 149 Silver tluoborate, 31 Simmons-Smith cyclopropanation, 110,223, 224,248,360,393.449,485 a and Sinensal, 17, 18 Sinularene, 429,443 Sirenin, 14 a-Snyderol, 75 P-Snyderol, 75 Snyderols, 80 Sodium acetylide, reaction with chloro epoxide, 34 Sodium benzenesulfinate, 253 Sodium bis (methoxyethoxy), aluminium hydride, 208 Sodium borohydride-cerium trichloride, 186 Sodium cyanoborohydride, 101, 153,505 in methylamine, 16 in presence of zinc bromide, 449 Solavetivone, 265,269 Spirovetivanes, 264 Stannic chloride, 88, 135,378,426 stereospecific cyclization with, 291 Stephens-Castro reaction, with 3-furylcopper, 35 Stereospecificsynthesis of olefins, from B-oxido phmphonium ylides and aldehydes, Stobbe condensation, 132 Stramonin B, 347,355 Sulphore, reductive cleavage of, 25 Sydowic acid, 35,44 a-Santalene, 249,253, 254 8-Santalene, 249 a-Santalol, 249, 252 8-Santalol, 249,258 a-Santonin 87,91, 118, 140, 144, 149 165, 34 I Sativene, 429,430,436,439 cis-Sativenediol, 429,440 Saussurea lactone, 90 Seco-cadinane, 46 Selenium dioxide, oxidation with retention of optical activity, 75 Selenium dioxide oxidation, 68, 126 Selenoxide elimination, 86 /3-Selinene, 129, 132 Sesquicarene, 14,317 Sesquichamaenol, 46 Sesquifenchene, 249,263 Sesquirosefuran, 25 Seychellene, 460,462,465 Taylorine, 228 Temsin, 90.92 a-Terpineol, 271 rrans-/3-Terpineol, 82 Terpinolene, 50 Terrestrol, Tetra-n-butylarnmonium oxalate (TBAO), 119 Tetrahydroeucaryone, 449 Tetrahydroligularenolide, 202,204 Tetramethylammonium acetate, 14I Thallium perchlorate, 396 Thallium trinitrate, 412 Thexylisobutylborane, 65 Thujopsadiene, 221,226 Thujopsene, 22 I, 226 Titanium tetrachloride, 128 p-Toluenesulfonylisoyanide, and potassium r-butoxide, 518 p-Toluenesulfonyl-S-methylcarbazate, sodium salt of, 326 Quadrone, 488 550 Index p-Toluenesulfonylmethyl isocyanide, 28I, 456 p-Tolyl Grignard reagent, 230 p-TolyUithium 23 I p-Tolylmagnesium bromide, addition to methylheptanone 36 Torreyal 28 Torreyol 166,168 Transfer hydrogenation 167 Tri-n-butylstannane 440 Trichodermin, 238 Trichodermol, 238 Trichodiene 238,246 Tricyclovetivene 473 Triethylphosphonoacetate anion, 47 3-Triethylsilyloxypentadienyllithium 470 Trimethylaluminum 364 Trimethyl phosphonoacetate, 82 3-Trimeih~lsilyiallymagnesiumbromide, 428 Trimethvlstannvllithium 121 conjugate a d h i o n of, 117 Triphenylphosphjne dibromide 269 Triphenyltin hydride 89.378 Tritylfluoroborate 79 Trityllithium, 335 Tuberiferine, 149.I5 I ur-Tumerone 35.38 Valencene, 180 Valerane, 2I5,2I7 Valeranone 2I5 Valeriana Waalichi, 259 VeUeral 38 I 384 Vellerolactone 381 384 Vernolepin, 90,93,95 Vernomenin 93 a-Vetispirene 265.266.269.277.283 8-Vetispirene, 265,269.277 Vetiver oil 290.473 p-Vetivone 264.265,281 Vinylacetyl chloride acylalion with 132 Vinyl cyclopropane rearrangement 442 I Vinyllithium addition of, 54 Vinylmagnesium bromide, copper catalyzed addition of, 90 101,329 retro-ene reaction, 89 Wacker oxidation, 415 Wadsworth-Emmons reaction, 181,363,403 Wagner-Meenvein rearrangement 25 I, 259 275.385,420 Warburganal, 170,175 Warburgiadione 192 West African soldier termite, 139 Whirligig water beetle, 24 White potatoes, fungus infection, 126 Wichterle annelation, 108 Wichterle reagent bromine homolog of, 130 Widdrol, 389 Wieland-Miescher ketone, 85 Wilkinson’s catalyst, 320,322,475 I *)-Winterin 172 , Wittig olefinalion, via @lactone, 36 Wittig reaction, 186,2I7 selective, 277 stereoselective, 23.34 Wolff-Kishner reduction, 386 WoltT rearrangement, 419 photochemical, 227.25s.29 I Xanthorrhizol, 35,42 a-Ylangene 452 8-Ylangene 452 Ylangocamphene 429 Mangocamphor, 250,429,436 Yomogin, 149,150 Zinc chloride 134 Zinc-copper couple in aqueous DMSO, 99 Zizane, 473 Zizaene 478 Zizanoic acid, 473 Zonarene 161,164 .. .Total Synthesis Of Natural Products, Volume Edited by John Apsimon Copyright © 1983, by John Wiley & Sons, Inc THE TOTAL SYNTHESIS OF NATURAL PRODUCTS The Total Synthesis of Natural Products. .. s ~ ~the synthesis of curcumene The synthesis is efficient and was easily adapted to a synthesis of isomer 56 , thus allowing an unambiguous assignment of structure for the natural product The. .. double bonds and 155 has a disubstituted double bond 0 \ H \ O\ I50 I/ U 151 153 154 155 Takahashi has reported a synthesis of dendrolasin which is summarized in Scheme 26.3 7The synthesis features