Progress in the Palladium‐Catalyzed Cyanation of Aryl Chlorides

Abstract
The development of new palladium catalysts for the cyanation of various aryl and heteroaryl chlorides is described. The combination of amine co‐catalysts with chelating phosphine ligands, for example, 1,4‐bis(diphenylphosphino)butane (dppb) or 1,5‐bis(diphenylphosphino)pentane (dpppe), allows an efficient cyanation of chloroarenes with simple potassium cyanide. General palladium‐catalyzed cyanation of nonactivated and deactivated chloroarenes is possible for the first time. Studies of the oxidative addition of aryl halides to palladium triphenylphosphine complexes in the presence and absence of amines suggest that the co‐catalyst is capable of preventing catalyst deactivation caused by the presence of excess cyanide ions in solution.