Addition of unactivated thiols to epoxides and oxetanes catalyzed by a rhenium-oxo complex

•Method for the catalytic addition of unactivated thiols to epoxides and oxetanes.•Reaction catalyzed by a rhenium(V)-oxo complex.•Regioselective synthesis of β- and γ-hydroxy thioethers.

A method for synthesizing β- and γ-hydroxy thioethers via addition of unactivated thiols to epoxides and oxetanes has been developed. This reaction is proposed to proceed through an unconventional mode of activation of the heterocycles. The transformation is catalyzed by ReO2I(PPh3)2 affording β- and γ-hydroxy thioethers in moderate to excellent yield with excellent regioselectivity.