Alkenylation of C(sp3)−H Bonds by Zincation/Copper‐Catalyzed Cross‐Coupling with Iodonium Salts

α-Vinylation of phosphonates, phosphine oxides, sulfones, sulfonamides, and sulfoxides has been achieved by selective C-H zincation and copper-catalyzed C(sp³ )-C(sp² ) cross-coupling reaction using vinylphenyliodonium salts. The vinylation transformation proceeds in high efficiency and stereospecificity under mild reaction conditions. This zincative cross-coupling reaction represents a general alkenylation strategy, which is also applicable for α-alkenylation of esters, amides, and nitriles in the synthesis of β,γ-unsaturated carbonyl compounds.