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

Abstract

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.