1,2-Sulfonylalkynylation of Alkynes to Access Sulfonyl-Substituted 1,3-Enyne Compounds via Nickel/Photoredox Dual Catalysis.

Alkyne difunctionalization provides a straightforward route to polysubstituted 1,3-enynes, especially through three-component reactions for structural diversification. Herein, we report a photoredox/nickel dual-catalyzed 1,2-sulfonylalkynylation of alkynes using readily available sodium sulfinates and bromoalkynes. This redox-neutral protocol delivers a diverse array of sulfonyl-substituted 1,3-enynes with excellent E-selectivity (>20:1) and broad functional group tolerance. Notably, internal alkynes are competent substrates, affording tetra-substituted enynes that are otherwise difficult to access stereoselectively. The sulfonyl group in the products serves as a versatile handle for downstream transformations, highlighting the synthetic utility of this method in medicinal chemistry.