AbstractThe selective introduction of a primary amino group into aromatic compounds is a desirable transformation, but is challenging due to competing double arylation. A catalyst generated from β‐methylnaphthyl (MeNAP) palladium bromide and the bulky ligand biphenyl‐diadamantylphosphine (AdBrettPhos) has been found to promote the amination even of non‐activated aryl chlorides with ammonium triflate within 30 min at 80 °C to the primary anilines. The efficiency of the protocol was evaluated in comparative experiments, its versatility documented by the synthesis of various primary anilines including drug‐like molecules.