Copper(I)‐Catalyzed Asymmetric 1,4‐Hydroarsination of α,β‐Unsaturated Compounds

Herein, a copper(I)‐catalyzed asymmetric 1,4‐hydroarsination of β‐substituted α,β‐unsaturated esters is achieved in moderate to excellent yields with high to excellent enantioselectivity, based on the proposed nucleophilic [Cu]‐AsPh2 species. As for α‐substituted α,β‐unsaturated esters, a 1,4‐hydroarsination/enantioselective protonation event occurs smoothly in satisfying results. Furthermore, β‐substituted α,β‐unsaturated ketone, α,β‐unsaturated amide, and α,β‐unsaturated phosphine sulfide are well applied in the present catalytic system. Finally, some control experiments show that HAsPh2 is activated through coordination with the copper(I) catalyst and HAsPh2 exhibits inferior soft Lewis basicity to HPPh2 in the presence of a copper(I)‐bisphosphine complex.