Palladium-Catalyzed Nitrile-Assisted C(sp3)-Cl Bond Formation for Synthesis of Dichlorides.

A palladium-catalyzed coupling procedure of alkenes with alkynylnitriles has been demonstrated for the synthesis of dichlorides. The reaction is the first example of nitrile-assisted C(sp3)-Cl formation promoted by coordination of a cyano group with an alkylpalladium(II) complex. The construction of a five-membered cycle intermediate successfully inhibits the β-hydride abstraction, resulting in direct C-Cl bond reductive elimination of alkylpalladium(II) chloride.