Photoelectrochemical Valorization of Nitromethane for Oxime Synthesis

The catalytic upgrading of bulk feedstock chemicals into value-added products represents a powerful approach in modern chemical synthesis. Herein, we describe an iron-catalyzed photoelectrochemical strategy that enables the efficient conversion of nitromethane (MeNO₂), an abundant industrial feedstock, into synthetically valuable nitric oxide (·NO). This proof-of-concept platform allows the direct synthesis of structurally diverse oximes from MeNO₂ and alcohols and exhibits broad functional group tolerance, including compatibility with carbonyl groups and acid-sensitive motifs such as esters and silyl ethers. Mechanistic investigations reveal that the iron catalyst plays a dual role: promoting radical deformylation of alcohols or ring-opening of cycloalkanols and mediating the conversion of MeNO₂ into ·NO.