Microbiological hydroxylation. Part XV. Hydroxylation in the terminal rings of mono- and di-oxygenated 5α-androstanes with the fungus Daedalea rufescens

Abstract

Mono- and di-ketones and keto-alcohols derived from 5α-androstane have been incubated with the fungus Daedalea rufescens, a Basidiomycete species not previously reported as a steroid hydroxylator. All but one of the dioxygenated substrates, and the monoketones with the keto-group in a central ring, are hydroxylated fairly rapidly. The cleanest hydroxylations occur with 7-oxygenated androstanes and lead to the 3β,16β-dihydroxy-derivatives.

Incubation of 3,3-ethylenedioxy-5α-androstan-7-one (in which hydroxylation is accompanied by reduction of the 7-keto-group) followed by hydrolysis of the product gives 7α,16β-dihydroxy-5α-androstan-3-one in 57% yield.