Modular synthesis of β-oxygen-containing sulfones from alkenes through hexatungstate-catalyzed cascade hydroxysulfenylation/selective oxidation†

β-Oxygen-containing sulfones are versatile building blocks in pharmaceuticals and the chemical industry. Despite notable advances in the reported methods, a sustainable and general catalytic method for preparing β-oxygen-containing sulfones remains elusive, due to the inherent reactivity disparities and notorious metal-catalyst-poisoning capability of sulfur nucleophiles. Here, we present a distinct multifunctional hexatungstate catalytic strategy for the synthesis of β-hydroxy sulfones and β-keto sulfones through a sequential hydroxysulfenylation of alkenes/selective oxidation process, utilizing a commerically available thiol and green hydrogen peroxide as the ‘oxy-sulfonylation reagent’. This method not only offers a practical route for delivering functionalized sulfones from readily available chemicals but is also sufficiently versatile to achieve late-stage oxysulfonylation of complex substrates and concise syntheses of bioactive molecules. Moreover, this modular methodology features a new mechanism, water as the sole byproduct, and mild reaction conditions free of hydroperoxide reductant.