Synthesis of C(1)-C(11) oxygen-bridged pregnanes

Tetrahedron Letters

Volumn 46, Issue 24, 2005, Pages 4235-4238

  Veleiro, Adriana S ^a   Taich, Paula J ^a   Alvarez, Lautaro D ^a   Di Chenna, Pablo H ^a   Burton, Gerardo ^a  

^a UNIVERSIDAD DE BUENOS AIRES   (Argentina)

Author keywords

1,11 Epoxypregnane; Diacetoxyiodobenzene; DIB; Remote functionalization reaction; Steroid

Indexed keywords

HYDROXYSTEROID; IODINE; IODOBENZENE; PREGNANE DERIVATIVE; STEROID HORMONE;

ARTICLE; CHEMICAL REACTION KINETICS; DRUG CONFORMATION; DRUG SYNTHESIS; PHOTOLYSIS;

EID: 19044388730     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2005.04.052     Document Type: Article

References (14)

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3. G.P. Vicent, M.C. Monteserín, A.S. Veleiro, G. Burton, C.P. Lantos, and M.D. Galigniana Mol. Pharmacol. 52 1997 749 753
4. A.S. Veleiro, R.E. Rosenstein, C.O. Jaliffa, M.L. Grilli, F. Speroni, and G. Burton Bioorg. Med. Chem. Lett. 13 2002 343 346
5. J. Kalvoda, and K. Heusler Synthesis 1971 501 526
6. P. de Armas, J.I. Concepción, C.G. Francisco, R. Hernández, J.A. Salazar, and E. Suárez J. Chem. Soc., Perkin Trans. 1 1989 405 411
7. Compound 5 was characterized by NMR and MS and was identical (mp) to that previously described in: J. Kalvoda, G. Anner, D. Arigoni, K. Heusler, H. Miner, O. Jeger, M.L. Mihailovic, K. Schaffer, and A. Wettstein Helv. Chim. Acta 44 1961 186 204
8. Compounds 6 and 7 were characterized by NMR and MS and were identical (mp) to those previously described in: M. Nussim, Y. Mazur, and F. Sondheimer J. Org. Chem. 29 1964 1120 1131
9. Compounds 8 and 11 were characterized by NMR and MS and were identical (mp) to those previously described in: J.E. Bridgeman, P.C. Cherry, A.S. Clegg, J.M. Evans, R.H. Jones, A. Kasal, V. Kumar, G.D. Meakins, Y. Morisawa, E.E. Richards, and P.D. Woodgate J. Chem. Soc. C 1970 250 257 Attempts to cyclize these compounds to the corresponding 1,11-epoxysteroids via a Michael addition of the 11-hydroxyl to the unsaturated ketone, were unsuccesful; both compounds were recovered unaltered after 18 h, upon treatment with either 1.2 M sodium methoxide/methanol or p-TsOH/dichloromethane
10. +, 5), 440 (7), 331 (13), 313 (45), 299 (4), 271 (11), 254 (59), 55 (100)
11. 3: C, 76.33; H, 9.15. Found C, 76.63; H, 9.09
12. + 418.2719. Found 418.2713
13. + 330.2195. Found 330.2201
14. Stability of the 1,11-epoxy bridges was tested for 10 and 14 in both acid (acetic acid/dichloromethane and HCl/methanol) and basic (KOH/methanol) media. Compound 10 was recovered unaltered after 24 h in both media, while 14 although stable in base, slowly decomposed to give 8 over a 24 h period in acid media