Heterocyclic steroids: Synthesis of steroidal selena, tellura, and thia lactones of estrane series

Article abstract of DOI:10.1016/0039-128X(95)00233-G

A successful approach in the synthesis of 3β-acetoxy-17a-selena-D-homo- 1,3,5(10)-estratrien-17-one (5), 3β-acetoxy-17a-tellura-D-homo-1,3,5(10)- estratrien-17-one (6), and 3β-acetoxy-17a-thia-D-homo-1,3,5(10)-estratrien- 17-one (7) was achieved from 3β-acetoxy-1,3,5(10)-estratrien-17-one (1). The baeyer-Villiger reaction of 3β-acetoxy-1,3,5(10)-estratrien-17-one (1) with perbenzoic acid afforded 3β-acetyxy-17a-oxa-D-homo-1,3,5(10)-estratrien-17- one (2), which on reaction with hydromic acid gave 3β-acetoxy-seco-13- bromo-1,3,5(10)-estratrien-16-oic acid (3). Treatment of bromo acid (3) with thionyl chloride gave 3β-acetovy-seco-13-bromo-1,3,5(10)-estratrien-17 acid chloride (4), whose reaction with Se and Te in the presence of sodium borohydride gave the desired products 5 and 6. Reaction of 3β-acetoxy-seco- 13-bromo-1,3,5(10)-estratrien-17 acid chloride (4) with sodium sulfide gave the thia lactone derivative.