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The desulfonylation of β‐arylketosulfones has been achieved in good to excellent yields by using 3‐W blue LEDs light, 1 mol‐% organic dye eosin Y bis(tetrabutylammonium salt) as photocatalyst, and diisopropylethylamine as reducing agent. Mechanistic studies demonstrate that oxidative quenching of the excited eosin Y by β‐arylketosulfones plays a crucial role in the present photoredox catalytic cycle.
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