Ad etailed study of regiospecific silylation, oxidation, and reductiono fs terols is reported. The differentr eactivity of 2a and 3a hydroxy groupsi sd emonstrated on a2 a,3a-dihydroxy-5a-pregnane-6,20-dionea samodel substrate. Ar egiospecific silylationo ft he 2a-alcohol occurred when silyl chloride was used under mild reaction conditions.The selective oxidation of one of the 2a,3a-diols by dimethyldioxirane or the Dess-Martin periodinaneled to amixture of a-hydroxyketones with high prevalence of 3,6,20-trione over 2,6,20-trione in the ratio 10:1. Ar egiospecific reduction of am odel substrateb yl ithium tri-tert-butoxyaluminium hydride gives the C6 alcohol.