Synthesis of 16-substituted 17-nor-13α-steroids and skeletal rearrangement of 17-nor-5α,13α-androstane-16α-carbonyl m-chlorobenzoyl peroxide

Abstract

The reaction of 17-nor-5α,13α-androstane-16β-carbonyl chloride with m-chloroperbenzoic acid led to a skeletal rearrangement that resulted in an abeo homodinorsteroid identical with one obtained by the reaction of 17-nor-5α-androstane-16β-carbonyl chloride with MCPBA, while the reaction of the isomeric 16α-carbonyl chloride with MCPBA gave 17-nor-5α,13α-androstan-16α-yl m-chlorobenzoate via a carboxy inversion of the initially formed acyl aroyl peroxide followed by decarboxylation. Several 16-substituted 13-epi-D-ring-norsteroids, including 16-nor-5α,13α-pregnan-20-one and its 17α-epimer, 17-nor-5α,13α-androstan-16α- and -16β-ol, and 17-nor-5α,13α-androstan-16-one, were synthesized, for the first time, from 5α,13α-androstan-17-one.