Abstract: | A new series of diarylvinylphosphine ligands was designed and synthesized. A catalyst system, consisting of the ligands and palladium species, effectively catalyzed the coupling reaction of aryl bromides and chlorides with amines to afford the corresponding products in good to excellent yields. The efficiency is likely derived from an interaction between the palladium center and the cis‐aryl moiety on the diarylvinylphosphine ligand stabilizing a catalytic intermediate during the coupling reaction. |