Oxyfunctionalization of Steroids by Dioxiranes: Site and Stereoselective C14 and C17 Hydroxylation of Pregnane and Androstane Steroids.

Dimethyldioxirane showed to be site and stereoselective in the CH oxygen insertion at C14 and C17 positions of pregnane and androstane steroids. Fine steric control and evidence for the influence of the carbonyl group on the dioxirane reactivity are reported.