A General Route to 3-Thiosubstituted Steroids via Copper-Catalyzed C–S Coupling

AbstractA convenient and efficient approach to 3-thiosubstituted androstanes has been developed. The formation of a C(sp2)–S bond was achieved through the Cu-catalyzed coupling of steroidal iododienes with a variety of S-nucleophiles, such as (het)aryl thiols and dithiocarbamates. A simple catalytic system comprising CuI without auxiliary ligands enabled the preparation of a library of target compounds in good to high yields. A moderate inhibitory activity against hormone-dependent cancer cell lines was demonstrated for representative 3-thiolated steroids.