Efficient Oxime Etherification of Inert C─H via Cl ⁻ ‐Mediated Photoelectrochemical Hydrogen Atom Transfer

This study demonstrates a WO₃ photoanode-based photoelectrochemical system capable of efficiently converting inert C─H bonds into oxime ethers via a chlorine-mediated hydrogen atom transfer mechanism with visible-light irradiation and low bias. The protocol features a broad substrate scope, excellent functional group compatibility, and synthetic yields up to 95% yield. Notably, light irradiation drives the reaction by generating a photocurrent at the anode while simultaneously triggering the photolysis of Cl₂ to produce highly reactive chlorine radicals. Hydrogen was simultaneously evolved at the cathode as the sole byproducts. Systematic investigations confirm the remarkable photoelectrochemical activity and cycling stability of the WO₃ photoanode, with gram-scale experiments and multiple characterization techniques verifying its practical applicability.