Total synthesis and complete assignment of the stereostructure of a cytotoxic bromotriterpene polyether (+)-aurilol

Journal of the American Chemical Society

Volumn 127, Issue 16, 2005, Pages 5806-5807

  Morimoto, Yoshiki ^a   Nishikawa, Yoshihiro ^a   Takaishi, Mamoru ^a  

^a Osaka Prefecture University   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BROMOTRITERPENE POLYETHER AURILOL; POLYETHER DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CYTOTOXICITY; DESULFURIZATION; EPOXIDATION; STEREOCHEMISTRY; STEREOISOMERISM; SYNTHESIS;

ANIMALS; APLYSIA; ETHERS; ETHERS, CYCLIC; HYDROCARBONS, BROMINATED; STEREOISOMERISM; TERPENES; TRITERPENES;

EID: 17744366394     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja050123p     Document Type: Article

References (34)

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4. For structural determinations of oxasqualenoids by total synthesis, see: (a) Kigoshi, H.; Ojika, M.; Shizuri, Y.; Niwa, H.; Yamada, K. Tetrahedron 1986, 42, 3789-3792. (b) Morimoto, Y.; Iwai, T.; Kinoshita, T. J. Am. Chem. Soc. 2000, 122, 7124-7125. (c) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 9328-9329. (d) Morimoto, Y.; Iwai, T.; Kinoshita, T. Tetrahedron Lett. 2001, 42, 6307-6309. (e) Kigoshi, H.; Itoh, T.; Ogawa, T.; Ochi, K.; Okada, M.; Suenaga, K.; Yamada, K. Tetrahedron Lett. 2001, 42, 7461-7464. (f) Morimoto, Y.; Takaishi, M.; Iwai, T.; Kinoshita, T.; Jacobs, H. Tetrahedron Lett. 2002, 43, 5849-5852.
5. For structural determinations of oxasqualenoids by total synthesis, see: (a) Kigoshi, H.; Ojika, M.; Shizuri, Y.; Niwa, H.; Yamada, K. Tetrahedron 1986, 42, 3789-3792. (b) Morimoto, Y.; Iwai, T.; Kinoshita, T. J. Am. Chem. Soc. 2000, 122, 7124-7125. (c) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 9328-9329. (d) Morimoto, Y.; Iwai, T.; Kinoshita, T. Tetrahedron Lett. 2001, 42, 6307-6309. (e) Kigoshi, H.; Itoh, T.; Ogawa, T.; Ochi, K.; Okada, M.; Suenaga, K.; Yamada, K. Tetrahedron Lett. 2001, 42, 7461-7464. (f) Morimoto, Y.; Takaishi, M.; Iwai, T.; Kinoshita, T.; Jacobs, H. Tetrahedron Lett. 2002, 43, 5849-5852.
6. For structural determinations of oxasqualenoids by total synthesis, see: (a) Kigoshi, H.; Ojika, M.; Shizuri, Y.; Niwa, H.; Yamada, K. Tetrahedron 1986, 42, 3789-3792. (b) Morimoto, Y.; Iwai, T.; Kinoshita, T. J. Am. Chem. Soc. 2000, 122, 7124-7125. (c) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 9328-9329. (d) Morimoto, Y.; Iwai, T.; Kinoshita, T. Tetrahedron Lett. 2001, 42, 6307-6309. (e) Kigoshi, H.; Itoh, T.; Ogawa, T.; Ochi, K.; Okada, M.; Suenaga, K.; Yamada, K. Tetrahedron Lett. 2001, 42, 7461-7464. (f) Morimoto, Y.; Takaishi, M.; Iwai, T.; Kinoshita, T.; Jacobs, H. Tetrahedron Lett. 2002, 43, 5849-5852.
7. For structural determinations of oxasqualenoids by total synthesis, see: (a) Kigoshi, H.; Ojika, M.; Shizuri, Y.; Niwa, H.; Yamada, K. Tetrahedron 1986, 42, 3789-3792. (b) Morimoto, Y.; Iwai, T.; Kinoshita, T. J. Am. Chem. Soc. 2000, 122, 7124-7125. (c) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 9328-9329. (d) Morimoto, Y.; Iwai, T.; Kinoshita, T. Tetrahedron Lett. 2001, 42, 6307-6309. (e) Kigoshi, H.; Itoh, T.; Ogawa, T.; Ochi, K.; Okada, M.; Suenaga, K.; Yamada, K. Tetrahedron Lett. 2001, 42, 7461-7464. (f) Morimoto, Y.; Takaishi, M.; Iwai, T.; Kinoshita, T.; Jacobs, H. Tetrahedron Lett. 2002, 43, 5849-5852.
8. For structural determinations of oxasqualenoids by total synthesis, see: (a) Kigoshi, H.; Ojika, M.; Shizuri, Y.; Niwa, H.; Yamada, K. Tetrahedron 1986, 42, 3789-3792. (b) Morimoto, Y.; Iwai, T.; Kinoshita, T. J. Am. Chem. Soc. 2000, 122, 7124-7125. (c) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 9328-9329. (d) Morimoto, Y.; Iwai, T.; Kinoshita, T. Tetrahedron Lett. 2001, 42, 6307-6309. (e) Kigoshi, H.; Itoh, T.; Ogawa, T.; Ochi, K.; Okada, M.; Suenaga, K.; Yamada, K. Tetrahedron Lett. 2001, 42, 7461-7464. (f) Morimoto, Y.; Takaishi, M.; Iwai, T.; Kinoshita, T.; Jacobs, H. Tetrahedron Lett. 2002, 43, 5849-5852.
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17. 3P, THF, rt, 4 h, 96%.
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21. For many similar examples implementing 5-exo-tet cyclizations, see: (a) Hanessian, S.; Cooke, N. G.; DeHoff, B.; Sakito, Y. J. Am. Chem. Soc. 1990, 112, 5276-5290. (b) Hashimoto, M.; Harigaya, H.; Yanagiya, M.; Shirahama, H. J. Org. Chem. 1991, 56, 2299-2311. (c) Ujihara, K.; Shirahama, H. Tetrahedron Lett. 1996, 37, 2039-2042. (d) Towne, T. B.; McDonald, F. E. J. Am. Chem. Soc. 1997, 119, 6022-6028. (e) Morimoto, Y.; Iwai, T.; Yoshimura, T.; Kinoshita, T. Bioorg. Med. Chem. Lett. 1998, 8, 2005-2010. (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
22. For many similar examples implementing 5-exo-tet cyclizations, see: (a) Hanessian, S.; Cooke, N. G.; DeHoff, B.; Sakito, Y. J. Am. Chem. Soc. 1990, 112, 5276-5290. (b) Hashimoto, M.; Harigaya, H.; Yanagiya, M.; Shirahama, H. J. Org. Chem. 1991, 56, 2299-2311. (c) Ujihara, K.; Shirahama, H. Tetrahedron Lett. 1996, 37, 2039-2042. (d) Towne, T. B.; McDonald, F. E. J. Am. Chem. Soc. 1997, 119, 6022-6028. (e) Morimoto, Y.; Iwai, T.; Yoshimura, T.; Kinoshita, T. Bioorg. Med. Chem. Lett. 1998, 8, 2005-2010. (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
23. For many similar examples implementing 5-exo-tet cyclizations, see: (a) Hanessian, S.; Cooke, N. G.; DeHoff, B.; Sakito, Y. J. Am. Chem. Soc. 1990, 112, 5276-5290. (b) Hashimoto, M.; Harigaya, H.; Yanagiya, M.; Shirahama, H. J. Org. Chem. 1991, 56, 2299-2311. (c) Ujihara, K.; Shirahama, H. Tetrahedron Lett. 1996, 37, 2039-2042. (d) Towne, T. B.; McDonald, F. E. J. Am. Chem. Soc. 1997, 119, 6022-6028. (e) Morimoto, Y.; Iwai, T.; Yoshimura, T.; Kinoshita, T. Bioorg. Med. Chem. Lett. 1998, 8, 2005-2010. (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
24. For many similar examples implementing 5-exo-tet cyclizations, see: (a) Hanessian, S.; Cooke, N. G.; DeHoff, B.; Sakito, Y. J. Am. Chem. Soc. 1990, 112, 5276-5290. (b) Hashimoto, M.; Harigaya, H.; Yanagiya, M.; Shirahama, H. J. Org. Chem. 1991, 56, 2299-2311. (c) Ujihara, K.; Shirahama, H. Tetrahedron Lett. 1996, 37, 2039-2042. (d) Towne, T. B.; McDonald, F. E. J. Am. Chem. Soc. 1997, 119, 6022-6028. (e) Morimoto, Y.; Iwai, T.; Yoshimura, T.; Kinoshita, T. Bioorg. Med. Chem. Lett. 1998, 8, 2005-2010. (f) Xiong, Z.; Corey, E. J. J. Am. Chem. Soc. 2000, 122, 4831-4832.
25. 3P, THF, rt, 4 h, 93%.
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34. In this reaction, all of the starting material 20 has been consumed, and the products other than 21 were inseparable and unidentifiable complex mixtures.