Malik Williams, Twinkle Patel, Matthew J. Moschitto
Sulfones are widely used sulfur‐VI motifs in pharmaceuticals. We report a hydrosulfonylation strategy that employs N ‐hydroxymethylphthalimide sulfones as versatile sulfinyl radical precursors. In the presence of tertiary amines, NHMP sulfones form electron donor–acceptor complexes that undergo light‐induced single‐electron transfer to generate sulfinyl radicals in the absence of a photocatalyst. The resulting radicals add efficiently to activated olefins, affording structurally diverse sulfones under mild conditions.