Herein, we developed palladium-catalyzed regio- and diastereoselective difluoromethylthiolation of acrylamides to form the Z-isomer product at room temperature. Using 8-aminoquinoline as a directing group, this protocol resulted in a high efficiency under mild reaction conditions and showed good functional group tolerances, which opens a novel synthetic methodology for accessing SCF2H-containing skeletons. Moreover, mechanistic studies were conducted to obtain insights into the reaction mechanism, and post-functionalization of the product reactions was performed.

The synthesis of thioether or selenoether through the cross‐coupling of C−S or C−Se bond is a high attractive research area due to the prevalence of thioether or selenoether in pharmaceutically active compounds, bioactive natural compounds, agrochemicals, and functional materials. Herein, a novel and general method has been developed for the construction of C−S or C−Se bonds using Katritzky pyridinium salts with disulfides or diselenides in the presence of nickel catalyst. This procedure exhibits remarkable functional group tolerance. Under mild reaction condition, a variety of thioethers and selenoethers is successfully and efficiently obtained through deaminative cross‐coupling.