title: Synthesis of 6,19-sulfamidate bridged pregnanes.
abstract: 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.
authors.affiliation: Departamento de Química Orgánica and UMYMFOR (CONICET-FCEN), Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, C1428EGA Buenos Aires, Argentina.
authors.forename: Fernando J
authors.initials: FJ
authors.lastname: Duran
authors.forename: Alberto A
authors.initials: AA
authors.lastname: Ghini
authors.forename: Philippe
authors.initials: P
authors.lastname: Dauban
authors.forename: Robert H
authors.initials: RH
authors.lastname: Dodd
authors.forename: Gerardo
authors.initials: G
authors.lastname: Burton
mesh_terms: D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D011278:Pregnanes / Q000138:chemical synthesis* / Q000737:chemistry; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D001952:Bridged-Ring Compounds; D011278:Pregnanes; D013451:Sulfonic Acids