Abstract
Transannular reaction of 6-dehydro-17α-methyltestosterone (I) and/or 4, 6-androstadiene-3, 17-dione (V) with hydrogen sulfide, in the presence of sodium methoxide, mainly afforded the corresponding 5α, 7α-disulfide, II and VI, respectively. Selective reduction of VI with sodium borohydride at room temperature below 30° yielded a mixture of 5α, 7α-epidithioandrostane-3α, 17β-diol (VIII) and its 3β isomer (IX). Further treatment of sodium borohydride at 60° converted dioldisulfides (VIII and IX) to diol-dithiols, which were isolated as tetraacetates (XIV and XV, respectively).
