Lewis Acid/Brønsted Acid Controlled Pd(II)-Catalyzed Chemodivergent Functionalization of C( sp 2 )-H Bonds with N-(Arylthio)i(a)mides.

An efficient and chemodivergent palladium-catalyzed thiolation (C-S) and imidation (C-N) of directing group-assisted C-H bonds have been accomplished employing N-(arylthio)imides in combination with either Brønsted acid or Lewis acid, respectively. Notable features of the developed methodologies include excellent diversity, high functional group tolerance, wide substrate scope, and use of a single N-S reagent. Importantly, the developed hypothesis was also successfully extended to the amidation of C-H bonds. A plausible mechanistic pathway was proposed based on the preliminary mechanistic study.