A facile one-pot synthesis of benzothiophenes via copper-catalyzed thiolation annulations of o-halostyrenes with NaSH

A copper-catalyzed thiolation annulation of o-halostyrenes with sodium hydrosulfide has been developed. In the presence of Cu(OTf)2 and 1,4-benzoquinone, a variety of 2-substituted benzothiophenes were prepared in moderate to good yields by tandem C-S bond forming reaction and hydrothiolation of olefins.