Ruthenium-catalyzed Oppenauer-type oxidation of 3β-hydroxy steroids. A highly efficient entry into the steroidal hormones with 4-en-3-one functionality

Journal of Organic Chemistry

Volumn 61, Issue 19, 1996, Pages 6587-6590

  Almeida, Maria L S ^a   Kocǒvský, Pavel ^b   Báckvall, Jan E̊ ^a  

^a UPPSALA UNIVERSITY   (Sweden)

^b UNIVERSITY OF LEICESTER   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

STEROID;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0029799135     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960361q     Document Type: Article

References (40)

1. Fieser, L. F.; Fieser, M. Steroids; Reinhold: New York, 1959.
2. (a) Kočovský, P.; Tureček, F.; Hájíček, J. Synthesis of Natural Products: Problems of Stereoselectivity; CRC Press: Boca Raton, FL, 1986; Vols. I and II.
3. (b) Smith, M. B. Organic Synthesis; McGraw-Hill: New York, 1994.
4. Corey, E. J.; Cheng, X.-M. The Logic of Chemical Synthesis; J. Wiley: New York, 1989; pp 23 and 385.
5. Taub, D. In The Total Synthesis of Natural Products; ApSimon, J., Ed.; J. Wiley: New York, 1973; Vol. 2, p 641.
6. (a) Lednicer, D.; Mitscher, L. A. The Organic Chemistry of Drug Synthesis; J. Wiley: New York, 1977; Vol. 1, p 155;
7. (b) 1980; Vol. 2, p 135;
8. (c) 1984; Vol. 3, p 81;
9. (d) 1980; Vol. 4, p 65.
10. Freid, J.; Edwards, J. A. Organic Reactions in Steroid Chemistry; Van Nostrand: New York, 1972.
11. For recent examples of application of both transition and nontransition metals in steroid chemistry, see, e.g.: (a) Urbanos, F.; Fernandez-Baeza, J.; Chaudret, B. J. Chem. Soc., Chem. Commun. 1991, 1739.
12. (b) Halcrow, M. A.; Urbanos, F.; Chaudret, B. Organometallics 1993,12,955.
13. (c) Urbanos, F.; Halcrow, M. A.; Fernandez-Baeza, J.; Dahan, F.; Labroue, D.; Chaudret, B. J. Am. Chem. Soc. 1993, 115, 3484.
14. (d) Horiguchi, Y.; Nakamura, E.; Kuwajima, I. J. Am. Chem. Soc. 1989, 111, 6257.
15. (e) KoËovsky, P.; Bains, R. S. J. Org. Chem. 1994, 59, 5439.
16. (f) Kočovský, P.; Šrogl, J.; Pour, M.; Gogoll, A. J. Am. Chem. Soc. 1994, 116, 186.
17. Rasmusson, G. H.; Arth, G. E. In Organic Reactions in Steroid Chemistry; Fried, J., Edwards, J. A., Eds.; Van Nostrand: New York, 1972; Vol. 1, p 222.
18. 1,8
19. Oppenauer, R. V. Rec. Trav. Chem. 1937, 56, 137.
20. Djerassi, C. Org. React. 1951, 6, 207.
21. 3Al.
22. 8,11,14 so that application of the Oppenauer oxidation in corticoid chemistry requires protection of the 17α-hydroxyl.
23. For a mechanistic overview of the D-homo rearrangement, see: Kirk, D. N.; Hartshorn, M. P. Steroid Reaction Mechanisms; Elsevier; Amsterdam, 1968; p 294.
24. (a) Keana, J. F. W.; Reich, R. Synth. Commun. 1972, 2, 323.
25. (b) Kirk, D. N.; Rajagopalan, M. S.; Varley, M. J. J. Chem. Soc., Perkin Trans. 1 1983, 2225.
26. (a) Bäckvall, J. E.; Chowdhury, R. L.; Karlsson, U.; Wang, G.-Z. In Perspectives in Coordination Chemistry; Williams, A. F., Floriani, C., Merbach, A. E., Eds.; Verlag Hel. Chim. Acta: Basel, 1992; p 463.
27. (b) Wang, G.-Z.; Bäckvall, J. E. J. Chem. Soc., Chem. Commun. 1992, 337.
28. (c) Karlsson, U.; Wang, G.-Z.; Bäckvall, J. E. J. Org. Chem. 1994, 59, 1196.
29. (d) Wang, G.-Z.; Andreasson, U.; Bäckvall, J. E. J. Chem. Soc., Chem. Commun. 1994, 1037.
30. (e) Bäckvall, J. E.; Chowdhury, R. L.; Karlsson, U. J. Chem. Soc., Chem. Commun. 1991, 473.
31. Almeida, M. L. S.; Beller, M.; Wang, G.-Z.; Bäckvall, J. E. Chem. Eur. J., in press.
32. Murahashi, S. L; Naota, T.; Hirai, N. J. Org. Chem. 1993, 58, 7318.
33. Shvo, Y.; Menashe, N. Organometallics 1991, 10, 3885.
34. Parish, E. J.; Honda, H.; Chitrakorn, S.; Livant, P. Lipids 1991, 26, 675.
35. Takatsuto, S.; Ikekawa, N. J. Chem. Soc., Perkin Trans. 1 1986, 2269.
36. Duddeck, H.; Rosenbaum, D.; Hani, M.; Elgamal, A.; Fayez, M. B. E. Magn. Reson. Chem. 1987, 25, 25.
37. Gravestock, M. B.; Morton, D. R.; Boots, S. G.; Johnson, W. S. J. Am. Chem. Soc. 1980, 102, 800.
38. Kirk, D. N.; Toms, H. C.; Douglas, C.; White, K. A.; Smith, K. E.; Latif, S.; Hubbard, R. W. P. J. Chem. Soc., Perkin Trans. 2 1990, 1567.
39. Hayamizu, K.; Ishii, T.; Yanagisawa, M.; Kamo. O. Magn. Reson. Chem. 1990, 28, 250.
40. Hofmeister, H.; Annen K.; Laurent, H.; Wiechert, R Lieb. Ann. Chem. 1987, 423.