Short synthesis of 16β-hydroxy-5α-cholestane-3,6-dione a novel cytotoxic marine oxysterol

Steroids

Volumn 71, Issue 7, 2006, Pages 599-602

  Denancé, Mickaël ^a   Guyot, Michèle ^b   Samadi, Mohammad ^a  

^a IPEM   (France)

^b CNRS   (France)

Author keywords

Boron catalyst; Diosgenin; Oxysterols; Selective reduction

Indexed keywords

16BETA [(TRIETHYLSILYL)OXY]CHOLEST 5 ENE 3ALPHA OL; 16BETA HYDROXY 5ALPHA CHOLESTANE 3,6 DIONE; 3BETA,16BETA BIS[(TRIETHYLSILYL)OXY]CHOLEST 5 ENE; ALCOHOL; CHOLEST 5 EN 3BETA,16BETA,27 TRIOL; CHOLESTANE DERIVATIVE; CYTOTOXIC AGENT; DIOSGENIN; MARINE TOXIN; OXOSTEROID; OXYSTEROL; UNCLASSIFIED DRUG; 16 HYDROXYCHOLESTANE 3,6 DIONE; 16-HYDROXYCHOLESTANE-3,6-DIONE;

ALGA; ARTICLE; CATALYSIS; DEOXYGENATION; DEPROTECTION REACTION; DRUG SYNTHESIS; HYDROGENATION; METABOLITE; OXIDATION; CHEMISTRY; CYTOLOGY; OXIDATION REDUCTION REACTION; RED ALGA; SYNTHESIS;

ALGAE;

ALGAE, RED; CATALYSIS; CHOLESTANONES; DIOSGENIN; MARINE TOXINS; OXIDATION-REDUCTION;

EID: 33646943820     PISSN: 0039128X     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.steroids.2006.03.002     Document Type: Article

References (25)

1. Schroepfer Jr. G.J. Oxysterols: modulators of cholesterol metabolism and other processes. Physiol Rev 80 (2000) 361-554
2. In: Guardiola F., Dutta P.C., Codony R., and Savage G.P. (Eds). Cholesterol and phytosterol oxidation products: analysis, occurrence and biological effects (2000), AOCS Press, Champaign, IL 1-394
3. Guardiola F., Codony R., Addis P.B., Rafecas M., and Boatella J. Biological effects of oxysterols: current status. Food Chem Toxic 34 (1996) 193-211
4. Gregorio-King C.C., Gough T., Van Der Meer G.J., Hosking J.B., Waugh C.M., McLeod J.L., et al. Mechanisms of resistance to the cytotoxic effects of oxysterols in human leukemic cells. J Steroid Biochem Mol Biol 88 (2004) 311-320
5. Panini S.R., and Sinensky M.S. Mechanisms of oxysterol-induced apoptosis. Curr Opin Lipidol 12 (2001) 529-553
6. Faulkner D.J. Marine natural products. Nat Prod Rep 19 (2002) 1-48 and previous reviews in this series cited therein
7. D'Auria M.V., Minale L., and Riccio R. Polyoxygenated steroids of marine origin. Chem Rev 93 (1993) 1839-1895
8. Ktari L., Blond A., and Guyot M. 16β-Hydroxy-5α-cholestane-3,6-dione, a novel cytotoxic oxysterol from the red alga Jania rubens. Bioorg Med Chem Lett 10 (2000) 2563-2565
9. Prakash O., Roy R., Bhakuni D.S., Wahidulla S., and Kamat S.Y. 2D-NMR Studies of a novel steroid from the red alga Acantophora spicifera. J Nat Prod 52 (1989) 686-692
10. Wahidulla S., D'Souza L., and Patel J. 5α-Cholestane-3 6-dione from the red alga Acantophora spicifera. Phytochemistry 26 (1987) 2864-2865
11. Bultel-Poncé V., Etahiri S., and Guyot M. New ketosteroids from the red alga Hypnea musciformis. Bioorg Med Chem Lett 12 (2002) 1715-1718
12. Marker R.E., Turner D.L., and Sterols C.X.V. Sapogenins. XLIV. The relation between diosgenin and cholesterol. J Am Chem Soc 63 (1941) 767-771
13. Arunachalam T., MacKoul Green N.M., and Caspi E. Synthesis of 26-halo-, 26-(phenylseleno)-, and 26-indolylcholesterol analogues. J Org Chem 46 (1981) 2966-2968
14. Williams J.R., Chai D., Bloxton J.D., Gong H., and Solvibile W.R. Synthesis of the aglycone of 26-O-deacetyl pavoninin-5. Tetrahedron 59 (2003) 3183-3188
15. Kim H.S., Oh S.H., Kim D.I., Kim I.C., Cho K.H., and Park Y.B. Chemical synthesis of 15-ketosterols and their inhibitions of cholesteryl ester transfer protein. Bioorg Med Chem 3 (1995) 367-374
16. 3 system. Tetrahedron Lett 40 (1999) 8919-8922
17. 3 catalyzed reduction of alcohols and cleavage of aryl and alkyl ethers with hydrosilanes. J Org Chem 65 (2000) 6179-6186
18. 13C NMR spectrum was identical to 6.
19. 3 see:
20. 3-catalyzed silation of alcohols: a mild, general method for synthesis of silyl ethers. J Org Chem 64 (1999) 4887-4892
21. 3 see:
22. 3-catalyzed hydrosilation of carbonyl functions. J Org Chem 65 (2000) 3090-3098
23. -HB(C6F5)3 complex to the primary silyl ether of 10. For more details of reaction mechanism, see Ref. [17].
24. Li S.H., and Li T.S. Steroidal 5-en-3-ones, intermediates of the transformation of steroidal 5-en-3b-ols to steroidal 4-en-3 6-diones oxidized by pyridinium dichromate and pyridinium chlorochromate. Steroids 63 (1998) 76
25. 1H NMR spectra of the isolated natural 1 shows some impurities, for this reason the reported [8] optical rotation of the natural material is slightly different from that of our synthetic substance (-2° versus +3.8°).