Anilines are potentially high‐value arylating agents, but are limited by the low reactivity of the strong C−N bond. We show that the reactive intermediate benzyne can be used to both activate anilines, and set‐up an aryl transfer reaction in a single step. The reaction does not require any transition metal catalysts or stoichiometric organometallics, and establishes a metal‐free route to valuable biaryl products by functionalizing the aniline C−N bond.
A transition metal‐free C−N arylation of easily accessible tertiary anilines enabled by bifunctional arynes is described. The reaction proceeds via a tandem nucleophilic attack of anilines to arynes, followed by a Smiles‐Truce rearrangement to furnish synthetically valuable and densely substituted biaryls. This protocol was further utilized for heterocyclic scaffolds, providing access to medium size azaheterocycles via n+2 carbon insertion.