Studies in Syntheses of Steroid Metabolites. I.

Several approaches to the synthesis of 3α, 11β-dihydroxy-5α-androstane-17-one (Vila) and 3α-hydroxy-5α-androstane-11,17-dione (XIIa) are discussed. The preferred route involves selective sodium borohydride reduction of 5α-androstane-3,11,17-trione (V) to 3β-hydroxy-5α-androstane-11,17-dione (VIa) and solvolysis of its tosylate (VIc) to afford a mixture of the ketoalcohol (XIIa) and the olefin (VIIIb). The latter is then converted, through the ketals (XIb) and (XIIIb), into the diolone (VIIa).