3p-Hydroxyandrost-5-en-17-one

The addition of two hydroxylic groups to the double bonds of unsaturated ketones is carried out by the same methods used for hydroxylations of alkenes (equations 71-83). As an example, hydroxylation of the double bond in 3p-hydroxyandrost-5-en-17-one is accomplished by treatment with one equivalent of osmium tetroxide in pyridine and subsequent reductive cleavage of the osmate ester with sodium bisulfite in aqueous pyridine (equation 442) [950. ... 

WiCHA, J., and K. Bal Synthesis of 25-Hydroxycholesterol from 3p-Hydroxyandrost-5-en-17-one. A Method for Stereospecific Construction of a Sterol Side-Chain. J. Chem. Soc. Chem. Comm. 1975,968. 

Thus it has been used as the first stage to obtain the starting material for the microbiological method with CSD-10 and simplified in more recent work leading to a synthesis of estrone in four steps from 3p-acetoxy-19-hydroxyandrost-5-en-17-one (ref. 116). Cholesteryl acetate was transformed by standard methods to the required androstane compound shown in the following scheme, which with hypobromous acid followed by lead tetraacetate and zinc reduction (cf. ref. 115) afforded the 19-hydroxy derivative. This with thallium nitrate in dioxan underwent loss of formaldehyde and hydration with water to afford the 19-nor-10p-alcohol in 70% yield. The diol obtained by saponification was converted by Oppenauer oxidation with N-methylpiperid-4-one as hydride aceptor (ref. 117) and afforded a 78% yield of the enone which was transformed almost quantitatively into... 

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