Aryne‐Enabled C−N Arylation of Anilines

Abstract 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.