Hypervalent Iodine‐Mediated Synthesis of Sulfones Using Organozinc Pivalates and Sulfinate Salts

Sulfones are key motifs in pharmaceuticals, agrochemicals, and functional materials, as well as versatile intermediates in synthesis. We report a general and practical protocol for sulfone synthesis that combines the group-transfer capability of hypervalent iodine reagents (HIRs)—particularly in situ-generated sulfonyl-containing HIRs—with organozinc pivalates. The method delivers a broad range of sulfones in high yields under mild conditions, exhibiting excellent functional group tolerance. Importantly, the method enables efficient sulfonylation using sodium bicyclo[1.1.1]pentane sulfinate (BCP–SO2Na), providing streamlined access to functionalized BCP-sulfones. The protocol further enables in situ sulfinate generation and one-pot transformations. These findings expand the scope of HIR-enabled umpolung reactivity and offer a practical, modular and operationally simple platform for accessing sulfones with broad synthetic and medicinally relevance.