SYNTHESIS OF 3-BETA,16-BETA,19-TRIHYDROXYANDROST-5-EN-17-ONE AND 16-BETA,19-DIHYDROXYANDROST-4-ENE-3,17-DIONE AND THEIR 19-OXO DERIVATIVES

3-beta,16-beta,19-Trihydroxyandrost-5-en-17-one (12) was synthesized from 5-alpha-bromo-3-beta-acetoxy-6-beta,19-epoxyandrostan-17-one (2) through acetoxylation at C-16-beta of the enol acetate 4 with lead tetraacetate and reductive cleavage of the epoxide ring with zinc dust yielding the 3-beta, 16-beta-diacetoxy-19-hydroxy steroid 11, followed by hydrolysis of the acetoxy groups with sulfuric acid. Jones oxidation of compound 11 followed by the acid hydrolysis gave the 19-oxo steroid 15. 5-alpha-Bromo-3-beta-hydroxy-16-beta-acetoxy-6-beta,19-epoxyandrostan-17-one (8), obtained by selective hydrolysis of the 3-formate 5 with ammonium hydroxide, was oxidized with Jones reagent to afford the 3-oxo steroid 16, which was converted into the 19-hydroxy derivative 17 by treatment with zinc dust. 16-beta, 19-Dihydroxandrost-4-ene-3, 17-dione (18) and its 19-oxo derivative 21 were obtained from compound 17 through a similar reaction sequence.