Redox-mediated domino electrosynthesis of N,N-dimethylformamide with industrial-relevant productivity and modularized cathodic integration

Abstract Electrosynthesis of N , N -dimethylformamide (DMF) combines sustainability with economic viability. However, its implementation is hindered by challenges in electrode engineering and reaction control. Herein, a redox-mediated domino electrosynthesis strategy is explored for efficient C–N coupling production of DMF over a binder-free single-molecule-integrated electrode engineered with designed cobalt phthalocyanines. This integrated electrode, featuring enhanced site accessibility and charge transfer capacity, exhibits high and selective methanol oxidation activity, initiating the domino process synergistically facilitated by in situ electrogenerated iodine as a redox mediator. The system operates stably at 50 mA cm –2 for over 150 h, achieving >90% Faradaic efficiency and a consistent DMF productivity of 839 μmol h –1 cm –2 . In a flow cell, pairing anodic DMF production with cathodic CO 2 -to-amide conversion yields industrial-scale DMF productivity up to 2.75 mmol h –1 cm –2 and gram-level amide-containing generic drug production at –200 mA cm –2 . Furthermore, comprehensive spectroscopic analysis and theoretical calculations elucidate a domino reaction sequence involving several key intermediates, namely *CH 2 O, iododiamine and iminium cation for DMF generation.