The Highly Efficient Suzuki–Miyaura Cross‐Coupling of (Hetero)aryl Chlorides and (Hetero)arylboronic Acids Catalyzed by “Bulky‐yet‐Flexible” Palladium–PEPPSI Complexes in Air

A series of Pd–PEPPSI complexes were designed and synthesized. The relationship between catalyst structure and properties was systematically investigated. It was revealed that “bulky‐yet‐flexible” C3 bearing ancenaphthyl backbone was a highly efficient precatalyst and could be successfully employed in Suzuki–Miyaura reactions of (hetero)aryl chlorides with (hetero)arylboronic acids at a low palladium loading in the presence of a weak inorganic base in air.