Synthesis of the sulfates derived from 5 alpha-cholestane-3 beta,6 alpha-diol

Three new steroid sulfates--3 beta-hydroxy-5 alpha-cholestan-6 alpha-yl sulfate, 6 alpha-hydroxy-5 alpha-cholestan-3 beta-yl sulfate, and 5 alpha-cholestan-3 beta,6 alpha-diyl disulfate--were synthesized. For the syntheses of the key intermediates, 3 beta-hydroxy-5 alpha-cholestan-6 alpha-yl acetate and 6 alpha-hydroxy-5 alpha-cholestan-3 beta-yl acetate, selective protection of hydroxy groups in 5 alpha-cholestane-3 beta,6 alpha-diol was necessary. This problem was solved by using a combination of acetyl, tetrahydropyranyl, and methoxymethyl protective groups, which represents a new approach leading to these hydroxy acetates. Sulfated derivatives of 5 alpha-cholestane-3 beta,6 alpha-diol are present in marine invertebrates and were synthesized for the purposes of biologic testing.