LAUSR

A new photocatalytic system was developed for carrying out desulfonylative α-oxyamination reactions of α-sulfonylketones in which α-ketoalkyl radicals are generated. The catalytic system is composed of benzimidazolium aryloxide betaines (BI+–ArO–), serving as visible light-absorbing electron donor photocatalysts, and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), playing dual roles as an electron donor for catalyst recycling and a reagent to capture the generated radical intermediates. Information about the detailed nature of BI+–ArO– and the photocatalytic processes with TEMPO was gained using absorption spectroscopy, electrochemical measurements, and density functional theory calculations.