Electrochemical Amination of Aryl Halides with NH3

Primary arylamines are the most pivotal class of organic motifs in pharmaceuticals, agrochemicals, ligands and natural products. Ammonia (NH3) is an ideal nitrogen source in terms of reactivity, atom economy, and environmental compatibility. Despite significant progress in the synthesis of primary arylamines, the development of a general method for rapid access to diversely functionalized primary arylamines is still urgent and necessary. Herein, we developed a method for the direct synthesis of primary arylamines through electrochemical amination of aryl halides with NH3. Notably, the weak nucleophilic reagent NH3 was directly used as an ammonia surrogate, allowing for efficient conversion of carbon‐halogen bonds to diverse primary arylamines with good functional group tolerance. A broad scope of functionalized primary arylamines has been achieved in moderate to excellent yields.