Thianthrenium Salts to Arynes: Base Promoted C−N Bond Construction

Abstract Amines are widely found in natural products, drugs and pesticides. We have proposed a base‐promoted method for synthesizing polysubstituted aromatic amines. The reaction does not necessitate the involvement of transition metals, provided that an equivalent base is employed. In this process, aryl thianthrenium salt serves as the precursor to arynes, which are subsequently distorted by the induction effect of different substituents. The attack of amine nucleophiles results in the formation of a series of multi‐substituted aromatic amine products.