Sesquiterpene Lactones: Total Synthesis of (±)-Vernolepin and (±)Vernomenin1,2

Journal of the American Chemical Society

Volumn 99, Issue 17, 1977, Pages 5773-5780

  Grieco, Paul A ^a   Nishizawa, Mugio ^a   Oguri, Tomei ^a   Burke, Steven D ^a   Marinovic, Nebojsa ^a  

^a UNIVERSITY OF PITTSBURGH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTINEOPLASTIC AGENT; LACTONE; SESQUITERPENE;

ARTICLE; CHEMISTRY; SYNTHESIS; TECHNIQUE;

ANTINEOPLASTIC AGENTS, PHYTOGENIC; CHEMISTRY; LACTONES; METHODS; SESQUITERPENES; SUPPORT, U.S. GOV'T, NON-P.H.S.; SUPPORT, U.S. GOV'T, P.H.S.;

EID: 0017777741     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00459a039     Document Type: Article

References (29)

1. For a preliminary account of this work see P. A. Grieco, M. Nishizawa, S. D. Burke, and N. Marinovic, J. Am. Chem. Soc., 98, 1612 (1976).
2. S. M. Kupchan, R. J. Hemingway, D. Werner, A. Karim, A. T. McPhail, and G. A. Sim, J. Am. Chem. Soc., 90, 3596 (1968).
3. S. M. Kupchan, R. J. Hemingway, D. Werner, and A. Karim, J. Org. Chem., 34, 3903 (1969).
4. T. A. Geissman and M. A. Irwin, Pure Appl. Chem., 21, 167 (1970);
5. S. M. Kupchan, Irwin, Pure Appl. Chem., 21, 227 (1970).
6. S. M. Kupchan, D. C. Fessler, M. A. Eakin, and T. A. Giacobbe, Science, 168, 376 (1970);
7. R. L. Hanson, H. A. Lardy, and S. M. Kupchan, Science, 168, 378 (1970);
8. S. M. Kupchan, T, J. Giacobbe, I. S. Krull, A. M. Thomas, M. A. Eakin, and D. C. Fessler, J. Org. Chem., 35, 3539 (1970).
9. For a review of methods for the construction of α-methylene lactones see P. A. Grieco, Synthesis, 67 (1975).
10. P. A. Grieco, J. A. Noguez, and Y. Masaki, Tetrahedron Lett., 4213 (1975);
11. P. A. Grieco, J. A. Noguez, and Y. Masaki, J. Org. Chem., 42, 495 (1977).
12. D. H. R. Barton, R. H. Hesse, M. M. Pechet, and E. Rizzardo, J. Am. Chem. Soc., 95, 2748 (1973); cf. D. Freeman, A. Acher, and Y. Mazur, Tetrahedron Lett., 261 (1975).
13. A. J. Birch, Q. Rev. Chem. Soc., 4, 69 (1950);
14. A. J. Birch and H. Smith, Rev. Chem. Soc., 12, 17 (1958);
15. H. O. House, “Modern Synthetic Reactions”, W. A. Benjamin, New York, N.Y. 1971, p 145;
16. H. Greenfield, R. A. Friedel, and M. Orchin, J. Am. Chem. Soc., 76, 1258 (1954).
17. For a review of selenium chemistry, see K. B. Sharpless, K. M. Gordon, R. F. Lauer, D. W. Patrick, S. P. Singer, and M. W. Young, Chem. Scr., BA, 9 (1975).
18. P. A. Grieco, Y. Yokoyama, S. Gilman, and M. Nishizawa, J. Org. Cham., 42, 2034 (1977).
19. The use of fert-butyl hydroperoxide in benzene containing triton B has previously been employed for epoxidation of α,β-unsaturated enones [N. C. Yang and R. A. Finnegan, J. Am. Chem. Soc., 80, 5845 (1958)]. Our attempts to convert 22 → 23 in benzene solution resulted in complete recovery of starting enone.
20. P. A. Grieco, K. Hiroi, J. J. Reap, and J. A. Noguez, J. Org. Chem., 40, 1450 (1975).
21. K. B. Sharpless and M. W. Young, J. Org. Chem., 40, 947 (1975);
22. P. A. Grieco, Y. Masaki, and D. Boxler, J. Am. Chem. Soc., 97, 1597 (1975).
23. P. A. Grieco, S. Gilman, and M. Nishizawa, J. Org. Chem., 41, 1485 (1976).
24. P. A. Grieco, J. A. Noguez, Y. Masaki, K. Hiroi, M. Nishizawa, A. Rosowsky, S. Oppenheim, and H. Lazarus, J. Med. Chem., 20, 71 (1977).
25. The synthesis of lactone 31 and the conversion of its corresponding diol to bisnorvernolepin and bisnorvernomenin has been reported [S. Danishefsky, T. Kitahara, P. F. Schuda, and S. Etheredge, J. Am. Chem. Soc., 98,3028 (1976)].
26. Recently the conversion of bisnorvernolepin to vernolepin has appeared [S. Danishefsky, T. Kitahara, R. McKee, and P. F. Schuda, J. Am. Chem. Soc., 98, 67 15 (1976)J.
27. P. A. Grieco and K. Hiroi, J. Chem. Soc., Commun., 1317 (1972).
28. P. A. Grieco, N. Marinovic, and M. Miyashita, J. Org. Chem., 40, 1670 (1975).
29. H. Bauer, Ber., 46, 92 (1913). We have found that the crude crystalline material obtained from the procedure of Bauer can be sublimed At 100 °C (0.2 mmHg), providing yellow crystals of o-nitrophenyl selenocyanate, mp 144 °C.