Dual Photoredox and Copper Catalysis: Enantioselective 1,2-Amidocyanation of 1,3-Dienes

Dual photoredox-transition-metalcatalysis has emerged asa powerful tool for the development of chemical transformations. However,its application in the selective difunctionalization of 1,3-dienesremains essentially unexploited. By the synergistic action of photoredoxand copper catalysts, we report herein an enantioselective 1,2-amidocyanationof 1,3-dienes. Visible-light irradiation of a chloroform solutionof conjugated dienes, N-Boc-amidopyridinium salts,and TMSCN in the presence of a catalytic amount of fac-Ir-(ppy)(3), Cu-(OTf)(2)center dot xH(2)O, and a chiral Box ligand affords three-component adductsin good to high yields with high regio- and enantioselectivities.A L*CuCN complex, fully characterized spectroscopically and confirmedby X-ray crystallographic analysis, is able to catalyze the transformation,therefore supporting an inner-sphere cyanide transfer pathway.

Automated summary

Dual photoredox-transition-metal catalysis is a powerful tool in chemical transformations, but its use in the selective difunctionalization of 1,3-dienes has been underexplored. Here, we report an enantioselective 1,2-amidocyanation of 1,3-dienes using synergistic action of photoredox and copper catalysts. The reaction proceeds under visible-light irradiation and produces three-component adducts with good to high yields and high regio- and enantioselectivities.