Synchronous skeletal rearrangement of D- nor-5α-androstane-16α- and -16β-carbonyl m-chlorobenzoyl peroxides

Abstract

The reaction of D-nor-5α-androstan-16β-carbonyl chloride, a steroidal cyclobutanecarbonyl chloride, with m-chloroperbenzoic acid leads via rearrangement to a C-homo-D-bisnor-steroid. In contrast, the 16α-isomer with m-chloroperbenzoic acid afforded the corresponding stable acyl aroyl peroxide which underwent competitively a carboxy-inversion reaction and the migration of the 13β-methyl group upon reflux in benzene.