Synthesis of 6,19-sulfamidate bridged pregnanes.
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.
Duran
Fernando J
FJ
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.
Ghini
Alberto A
AA
Dauban
Philippe
P
Dodd
Robert H
RH
Burton
Gerardo
G
D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D011278:Pregnanes / Q000138:chemical synthesis* / Q000737:chemistry; D013451:Sulfonic Acids / Q000737:chemistry*
D001952:Bridged-Ring Compounds; D011278:Pregnanes; D013451:Sulfonic Acids