Total synthesis of (+)-breynolide

Tetrahedron Letters

Volumn 40, Issue 1, 1999, Pages 9-12

  Burke, Steven D ^a   Letourneau, Jeffrey J ^a,b   Matulenko, Mark A ^a,c  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

^b PHARMACOPEIA INC   (United States)

^c ABBOTT LABORATORIES   (United States)

Author keywords

Epoxides; Oxygen heterocycles; Rearrangements; Sulfur heterocycles

Indexed keywords

BREYNOLIDE; EPOXIDE; GLYCOSIDE; HETEROCYCLIC COMPOUND; UNCLASSIFIED DRUG;

ARTICLE; CRYSTAL STRUCTURE; DRUG ISOLATION; DRUG SYNTHESIS; EPOXIDATION; GENE REARRANGEMENT; HYPOCHOLESTEROLEMIA; NONHUMAN; OXIDATION; PROTON TRANSPORT; STEREOCHEMISTRY; X RAY ANALYSIS;

EID: 0032890256     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)80004-X     Document Type: Article

References (33)

1. (a) Sakai, F.; Ohkuma, H.; Koshiyama, H.; Naito, T.; Kawaguchi, H. Chem. Pharm. Bull. 1976, 24, 114.
2. (b) Koshiyama, H.; Hatori, M.; Ohkuma, H.; Sakai, F.; Imanishi, H.; Ohbayashi, M.; Kawaguchi, H. Ibid. 1976, 24, 169.
3. (c) Sasaki, K.; Hirata, Y. Tetrahedron Lett. 1973, 2439.
4. (d) Ohkuma, H.; Tsuno, T.; Konishi, M.; Naito, T.; Kawaguchi, H. Chem. Pharm. Bull. 1991, 39, 942.
5. (e) Smith, A. B., III; Keenan, T. P.; Gallagher, R. T.; Furst, G. T.; Dormer, P. G. J. Org. Chem. 1992, 57, 5115.
6. Trost, W. IRCS Med. Sci. 1986, 14, 905.
7. For leading references to phyllanthocin isolation and synthetic studies see: Burke, S. D.; Cobb, J. E.; Takeuchi, K. J. Org. Chem. 1990, 55, 2138.
8. (a) Nishiyama, S.; Ikeda, Y.; Yoshida, S.; Yamamura, S. Tetrahedron Lett. 1989, 30, 105.
9. (b) Williams, D. R.; Jass, P. A.; Allan, Tse, H.-L.; Gaston, R. D. J. Am. Chem. Soc. 1990, 112, 4552.
10. (c) Smith, A. B., III; Empfield, J. R.; Rivero, R. A.; Vaccaro, H. A. J. Am. Chem. Soc. 1991, 113, 4037.
11. (d) Smith, A. B., III; Empfield, J. R.; Rivero, R. A.; Vaccaro, H. A.; Duan, J. J.-W.; Sulikowski, M. M. J. Am. Chem. Soc. 1992, 114, 9419.
12. (e) Martin, S. F.; Daniel, D. Tetrahedron Lett. 1993, 34, 4281.
13. (f) Linderman, R. J.; Cutshall, N. S.; Becicka, B. T. Tetrahedron Lett. 1994, 35, 6639.
14. (g) Martin, S. F.; Anderson, B. G.; Daniel, D.; Gaucher, A. Tetrahedron 1997, 53, 8997.
15. (a) Corey, E. J.; Chen, C.-P.; Reichard, G. A. Tetrahedron Lett. 1989, 30, 5547.
16. (b) Corey, E. J.; Bakshi, R. K.; Shibata, S.; Chen, C.-P.; Singh, V. K. J. Am. Chem. Soc. 1987, 109, 7925.
17. Henbest, H. B. Proc. Chem. Soc. 1963, 159.
18. (a) Murata, S.; Suzuki, M.; Noyori, R. J. Am. Chem. Soc. 1979, 101, 2738.
19. (b) Murata, S.; Suzuki, M.; Noyori, R. Bull. Chem. Soc. Jpn. 1982, 55, 247.
20. A ratio of 6.8:1.0 (β:α) of epoxide diastereomers was obtained in the epoxidation reaction. The epoxide diastereomers were separable by flash column chromatography.
21. Burke, S. D.; Fobare, W. F.; Pacofsky, G. J. J. Org. Chem. 1983, 48, 5221 and references cited therein.
22. Bartlett, P. A.; Pizzo, C. F. J. Org. Chem. 1981, 46, 3896.
23. Mancuso, A. J.; Huang, S.-L.; Swern, D. J. Org. Chem. 1978, 43, 2480.
24. Van Rheenen, V.; Kelly, R. C.; Cha, D. Y. Tetrahedron Lett. 1976, 1973.
25. For a related tetrahydrothiophene construction, see: Whitney, R. A. Can. J. Chem. 1983, 61, 1158.
26. Corey, E. J.; Gras, J.-L.; Ulrich, P. Tetrahedron Lett. 1976, 809.
27. Concern arose that the p-MPM ether (suitable for the glycolate Claisen rearrangement and tetrahydrothiophene construction) might not survive the upcoming spiroketalization reaction because of unpublished observations in our group of acid lability of p-MPM ethers. See also Kocienski, P. J. Protecting Groups; Thieme: 1994, p 52. This switch maintains the differential protection of the C(3), C(6) and C(11) secondary hydroxyls in 16, necessary for elaboration to breynogenin and breynin A, which bears a trisaccharide glycosidic attachment at C(3).
28. (a) Boeckman, R. K.; Bruza, K. J. Tetrahedron Lett. 1977, 4187.
29. (b) Boeckman, R. K.; Bruza, K. J. Tetrahedron 1981, 37, 3997.
30. Because the spiroketal diastereomers were not readily separable, they were carried forward as a mixture to 16, which was isolated and fully characterized. The minor diastereomeric diacetates were not individually characterized or enumerated.
31. Brown, H.C.; Krishnamurthy, S. J. Am. Chem. Soc. 1972, 94, 7159.
32. Nakajima, N.; Abe, R.; Yonemitsu, O. Chem. Pharm. Bull. 1988, 36, 4244.
33. 13C NMR data of an authentic sample kindly provided by Professors A. B. Smith, III and D. R. Williams, whom we thank.