Readily accessible -sulfonylaminophthalimides were developed to be efficient sulfonyl radical precursors upon being treated with a base/oxidant under mild conditions. The method was applied to the oxysulfonylation of olefins, providing β-ketosulfones and isobenzofurans stereoselectively. On the basis of control experiments, density functional theory calculations, and the literature, a plausible radical mechanism was proposed. The findings offered a chance to develop novel radical precursors based on diversely substituted -aminophthalimides, which might establish a universal mild approach for the generation of various radicals.
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