Steroids and Steroidases: Iii. Dicyclohexylcarbodiimide–dimethyl Sulfoxide Oxidations of Alcohols and Thiols

A survey of methods for the preparation of acid- and base-labile steroid Δ5-3-ketones showed that oxidation of the appropriate Δ5-3β-alcohols with dicyclohexylcarbodiimide–dimethyl sulfoxide (Moffatt reagent) was the most satisfactory, giving yields of 60–70% of the required ketones with little or no isomerization to the corresponding Δ4-3-ketones. From the oxidation of 3β-hydroxyandrost-5-en-17-one, the product of a Pummerer rearrangement, 3β-(methylthiomethoxy)-androst-5-en-17-one, was isolated. The Moffatt reagent also was convenient for the oxidation of thiols to the corresponding disulfides.