Isolation and structure elucidation of new radical oxidation products of 5-hydroxy steroids

Three new products have been isolated from the lead-tetraacetate version of the hypoiodite oxidation of 3β,17β-diacetoxy-5-hydroxy-5α-androstane. Along with the expected 1(10)-unsaturated 5,10-seco steroidal 5-ketones, the fragmentation reaction gave two epimeric C-4 iodides. Their structural assignment was based on X-ray data of one of them ((4R,10S)-4-iodo-3β,17β-diacetoxy-5,10-secoandrostan-5-one). The third new product was found to be the 5β,6β-epoxide resulting from the dehydration of the tertiary alcohol followed by epoxidation of the intermediate Δ5-olefin.