Unlocking the Potential of Tris(Pentafluorophenyl)Borane in Reductive Desulfurization of Thioamides With Silane

Selective conversion of a functional group to a high-value product, namely defunctionalization, is an important procedure in synthetic chemistry. Herein, we report the first transition metal-free desulfurization of thioamides under relatively mild reaction conditions. The catalytic reaction proceeds with the selective cleavage of the C═S bonds of thioamides to furnish the corresponding amines in good to excellent yields with B(C₆F₅)₃ and PhSiH₃. The protocol is simple, does not require any additives, and encompasses a broad substrate scope with chemoselective reduction of vulnerable functional groups. To understand the mechanism, several control studies and detailed computational calculations were performed.