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).