A Pd‐catalyzed fluoroarylation of gem‐difluoroalkenes with aryl halides is reported. By taking advantage of the in situ generated α‐CF3‐benzylsilver intermediates derived from the nucleophilic addition of silver fluoride to gem‐difluoroalkenes, this strategy bypasses the use of a strong base, thus enabling a mild and general synthetic method for ready access to non‐symmetric α,α‐disubstituted trifluoroethane derivatives.

Herein, we report a highly efficient and practical method for pyridine‐derived heterobiaryl synthesis through palladium‐catalyzed electrophilic functionalization of easily available pyridine‐derived quaternary phosphonium salts. The nice generality of this reaction was goes beyond arylation, enabling facile incorporation of diverse carbon‐based fragments, including alkenyl, alkynyl, and also allyl fragments, onto the pyridine core. Notably, the silver salt additive is revealed to be of vital importance for the success of this transformation and its pivotal role as transmetallation mediator, which guarantees a smooth transfer of pyridyl group to palladium intermediate, is also described.