A ruthenium catalyzed oxidation of steroidal alkenes to enones

Tetrahedron Letters

Volumn 37, Issue 20, 1996, Pages 3429-3432

  Miller, Ross A ^a   Li, Wenjie ^a   Humphrey, Guy R ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

OXOSTEROID;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; OXIDATION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030013712     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00586-2     Document Type: Article

References (22)

1. Miller, R. A., Humphrey, G. R., Thompson, A. S Tetrahedron Lett. 1995, 36, 7949.
2. Bakshi, R.K., Patel, G.F., Rasmusson, G. H., Baginsky, W.F., Cimis, G., Ellsworth, K., Chang, B., Bull, H., Tolman, R.L., Harris, G.H. J. Med. Chem. 1994, 3871.
3. a. Pearson, A.J., Chen, Y.S., Han, G.R., Hsu, S.Y., Ray, T. J. Chem. Soc., Perkin Trans. 11985, 267;
4. b. Muzart, J. Tetrahedron Lett., 1987, 27, 4665;
5. c. Dauben, W.G., Lorber, M., Fullerton, D.S., J. Org. Chem. 1969, 34, 3587;
6. d. Fullerton, D.S., Chen, C.-M., Syn. Commun. 1976, 217;
7. e. Parish, E.J., Wei, T.-Y., Synth. Commun. 1987, 17, 1227;
8. f. Chidambaram, N., Chandrasekaran, S., J.Org. Chem. 1987, 52, 5048.
9. a. Kimura, M., Muto, T. Chem Pharm Bull. 1980, 28, 1836;
10. b. Prousa, R., Schonecker, B. J. Prakt. Chem. 1991, 5, 333;
11. c. Foricher, J., Furbringer, C. Pfoertner, K. US patent 5,030,739.
12. a. Agarwal, D.D., Jain, R., Sangha, P., Rastogi, R. Indian J Chem. 1993, 32B, 381;
13. b. Tanaka, M., Kobayshi, T., Sakakura, T., Angew. Chem. Int. Ed. 1984, 23, 433;
14. c. Murahashi, S.I., Naota, T. Synthesis 1993, 433.
15. d. Murahashi, S.I., Oda, Y., Naota, T., Kuwabara, T. Tetrahedron Lett. 1993, 34, 1299.
16. e. Murahashi, S.-I., Oda, Y., Naota, T. Chem Lett., 1992, 2237.
17. For a discussion of TBHP oxidations of alkenes under metal catalysis, see Sharpless, K.B., Verhoeven, T.R. Aldrichimica Acta 1979, 12, 63.
18. T = 18 ,19 min . To the reaction mixture was added 550 mL methyl ethyl ketone 390 mL water, and 39 gms sodium sulfite. The mixture was heated to 70 °C until the enedione 17 is gone (3 hrs). The reaction mixture was cooled to RT, then filtered through a pad of Solka-Flok to remove the ruthenium salts. The clear solution was separated and the organic layer washed with 100 mL 1% brine. The organic solution was turned over to 350 mL of heptane, cooled to -5°C and filtered, washing twice with 150 mL of cold heptane. After drying, the product was obtained in 69 % yield (53.7 gms) as an off-white solid whose spectra was consistent with the literature(reference 3). Mother liquor losses were 4.5 gm/6%.
19. Kumar, V., Amann, A., Ourisson, G., Luu, B. Synth. Commun. 1987, 17(11), 1279.
20. The peroxides were made according to the procedure in reference 4c.
21. 4 calcd 456.3239 found 456.3266 ± 2.7amu.
22. +] 534.