Taming Sulfate Radical for Anti-Markovnikov Alkene Hydrosulfation

The ability to tame reactive oxygen species as oxygen sources enables a distinct reaction mode and streamlines formidable molecule synthesis. In this context, sulfate radicals (SO₄^•-) are potent yet underutilized intermediates for alkene functionalization, yielding valuable organosulfates prevalent in biomolecules, pharmaceuticals, and detergents. However, their high redox potential favors electron transfer over functional group addition. We herein present a strategy to harness SO₄^•- for anti-Markovnikov hydrosulfation via synergistic "redox-recognition" and polar effects. A hydrogen donor with tailored redox potential precisely controls the reductive liberation of SO₄^•- from persulfates, simultaneously suppressing detrimental over-reduction and providing an electrophilic hydrogen source to trap nucleophilic alkyl radical after SO₄^•- addition to alkene. This protocol provides a powerful tool to synthesize structurally diverse organosulfates and anti-Markovnikov hydration products with their readily hydrolyzable nature. Remarkably, precise modulation of SO₄^•- reactivity permits switchable pathways─selective alkene hydrosulfation or traditional alcohol <i>O</i>-sulfurylation─even in substrates containing both functional groups.