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 chemical industry. Despite notable advancements in reportedmethods, a sustainable and general catalytic method for the preparation of 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 also showcases its versatility through late-stage oxysulfonylation of complex substrates and concise syntheses of bioactive molecules. Moreover, this modular methodology features hydroperoxide reductant free, mild reaction conditions, water as the sole byproduct and new mechanism.