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(C 6 F 5 ) 3 and PhSiH 3 . 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.