Mechanistic Understanding of the Unexpected Meta Selectivity in Copper-Catalyzed Anilide C–H Bond Arylation

DFT calculations suggest that the unexpected meta product in the copper-catalyzed arylation of anilide is formed via a Heck-like four-membered-ring transition state involving a CuIII–Ph species. A competitive electrophilic substitution mechanism delivers the ortho product when a methoxy group is present at the meta position of pivanilide. A series of experiments including kinetic studies support the involvement of a CuI catalyst.