Abstract: | A direct and enantioselective oxidative cross‐coupling of racemic 2,2‐diarylacetonitriles with electron‐rich (hetero)arenes has been described, which allows for efficient construction of triarylmethanes bearing all‐carbon quaternary stereocenters with excellent chemo‐ and enantioselectivity. The reaction has an excellent functional group tolerance, and exhibits a broad scope with respect to both 2,2‐diarylacetonitrile and (hetero)arene components. The rich chemistry of the cyano group allows for facile synthesis of other valuable chiral triarylmethanes bearing all‐carbon quaternary centers that are otherwise difficult to access. |