Synthesis of 6,19-Sulfamidate Bridged Pregnanes

F. J. DURÁN; A. A. GHINI; P. DAUBAN; R. H. DODD; G. BURTON

JOURNAL OF ORGANIC CHEMISTRY

American Chemical Society

Año: 2005 vol. 70 p. 8613 - 8616

0022-3263

Conformationally restrained substituted pregnane-20-one derivatives were obtained by an intramolecular nitrene addition onto a C-5/C-6 double bond involving a tethered C-19 sulfamoyl moiety. The resulting aziridine underwent regioselective nucleophilic ring opening at C-5 at room temperature with cyanide, fluoride, and acetate. In the isolated case of acetate, a reversal of regioselectivity was observed at higher temperatures, a result attributed to a rearrangement process involving aziridine ring opening at the C-5 position and subsequent migration of the acetyl moiety to C-6.