Cascade Electrosynthesis of Aryl Imides and Sulfonimides From N 2 via Integrated Nitrogen Fixation and C─N/S─N Bond Formation

Direct synthesis of organonitrogen compounds from dinitrogen (N 2 ) remains a formidable challenge because N 2 ‐to‐C─N bond formation requires nitrogen fixation to be coupled with selective functionalization of N 2 ‐derived intermediates before their termination as ammonia. Herein, we report a cascade electrochemical strategy that converts N 2 into aryl imides and aryl sulfonimides in a gas‐diffusion electrochemical flow cell. Under proton‐donor‐free conditions, electrochemically generated Li 3 N is intercepted by acyl or sulfonyl chlorides, enabling one‐pot synthesis of aryl imides and sulfonimides from N 2 in yields up to 57%. This represents a notably high yield for direct N 2 ‐derived organonitrogen synthesis. This work couples N 2 fixation and C─N/S─N bond formation, expanding electrochemical nitrogen fixation beyond ammonia synthesis toward direct construction of value‐added C─N/S─N bonds.