Local pH Control Promotes Oxygen-Atom Transfer Electrosynthesis

Abstract Control of the local reaction environment at electrified interfaces is central to electrocatalysis, yet this principle has rarely been integrated into electro-organic synthesis. Electro-organic transformations are not governed by electron transfer alone; reaction turnover is often coupled to ion transfer and, in particular, proton transfer across aqueous, mixed, and nonaqueous media. Under high-rate operation, these fluxes polarize proton activity near electrodes. Although such concentration polarization is expected to be widespread and consequential, it has been largely neglected in electrosynthesis design. Here we establish a mechanistically distinct, oxygen-driven electrosynthetic pathway for Baeyer–Villiger oxidation (BVO) and use it to develop a local-pH design framework for electro-organic synthesis. Isotope labeling shows that O2 supplies the inserted oxygen atom, and rad…