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.