In this study, atom- and step-efficient electrochemical coupling of nitroso compounds with ammonium N-(methoxy)nitramide, furnishing methoxy-NNO-azoxy compounds, is reported. The developed protocol employs a divided electrochemical cell, proceeds under constant-current electrolysis conditions, and is applicable to aromatic, heterocyclic, and aliphatic nitroso compounds. The versatility of the developed electrochemical coupling method was demonstrated by comparing it with chemical approaches on various substrates.

An atom- and step-economical electrochemical method for the synthesis of aliphatic nitro- NNO -azoxy compounds from the corresponding nitroso compounds was developed employing ammonium dinitramide, a prospective green oxidant for aerospace propulsion applications, as both electrolyte and source of a =NNO ₂ group. The developed method is green, practical, and scalable due to constant current electrolysis in an undivided cell at high current densities. Synthesized products demonstrated pronounced NO-donor activity and fungicidal activity against phytopathogenic fungi.