Microbiological hydroxylation of steroids. Part IV. The pattern of dihydroxylation of mono-oxygenated 5α-androstanes with cultures of the fungus Calonectria decora

Abstract

The work is concerned with the relation between the pattern of the dihydroxylation by Calonectria decora of mono-oxygenated 5α-androstane derivatives (mainly ketones), and the position of the oxygen function in the substrate. Terminal ring ketones (3, 4, 16, and 17) are converted, in useful yields, into one or two dihydroxy-ketones. (Ring B and C ketones are much less satisfactory as substrates.) The structures of most of the products followed from spectrometric investigations; this approach was supplemented by chemical correlations where necessary The two hydroxy-groups are introduced on to carbon atoms separated by about 4 Å from one another. The distances of these centres from the carbonyl group are more variable, although with the 3-,4-,16-, and 17-ketones the correspondence is gratifyingly close and may have predictive value.