A Photocatalytic System Composed of Benzimidazolium Aryloxide and Tetramethylpiperidine 1-Oxyl to Promote Desulfonylative α-Oxyamination Reactions of α-Sulfonylketones

[Image: see text] 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.