Stereoselective Synthesis of Vinyl Sulfones via Photoredox/Nickel Dual Catalysis

• 1、College of Chemistry, Chemical Engineering of Chongqing University, Chongqing 401331

Abstract：In this paper, a heterogeneous photoredox/nickel dual catalytic system for the efficient and highly stereoselective synthesis of vinyl sulfones via alkynes sulfonylation is described. The three-component reaction of sodium p-toluenesulfinate, aryl iodides, and aryl alkynes proceeds under mild conditions to afford the desired products with excellent stereocontrol. Through systematic optimization of reaction parameters, the (E)-vinyl sulfones were obtained in up to 94% yield with outstanding stereoselectivity (E/Z> 98:2). This protocol demonstrates broad substrate scope, accommodating various aryl iodides and aryl alkynes bearing diverse electronic substituents to furnish a wide range of aryl, heteroaryl, and functionalized vinyl sulfones in 74-90% yields. Importantly, natural product derivatives including L-tyrosine, D-glucose, and estrone are well tolerated, enabling efficient late-stage modification of complex molecules. Control experiments confirm that the photocatalyst, nickel complex, ligand, light irradiation, and inert atmosphere are essential for the reaction. Based on experimental observations, a plausible mechanism involving photogenerated electron-hole pairs, sulfonyl radicals, and a Ni(I)/Ni(II) catalytic cycle is proposed. This study provides a reliable approach to configurationally defined vinyl sulfones, laying a solid foundation for subsequent stereospecific transformations.

Keywords： Organic chemistry Vinyl sulfones Heterogeneous photocatalysis Stereoselective