Three-Component Aminoarylation of Electron-Rich Alkenes by Merging Photoredox with Nickel Catalysis

A three-component 1,2-aminoarylation of vinyl ethers, enamides, ene-carbamates and vinyl thioethers by synergistic photoredox and nickel catalysis is reported. 2,2,2-Trifluoroethoxy carbonyl protected alpha-amino-oxy acids are used as amidyl radical precursors. anti-Markovnikov addition of the amidyl radical to the alkene and Ni-mediated radical/transition metal cross over lead to the corresponding 1,2-aminoarylation product. The radical cascade, which can be conducted under practical and mild conditions, features high functional group tolerance and broad substrate scope. Stereoselective 1,2-aminoarylation is achieved using a L-(+)-lactic acid derived vinyl ether as the substrate, offering a novel route for the preparation of protected enantiopure alpha-arylated beta-amino alcohols. In addition, 1,2-aminoacylation of vinyl ethers is achieved by using an acyl succinimide as the electrophile for the Ni-mediated radical coupling.

Automated summary

A three-component 1,2-aminoarylation reaction is reported, utilizing synergistic photoredox and nickel catalysis. The method shows high functional group tolerance and broad substrate scope, allowing for the stereoselective synthesis of enantiopure alpha-arylated beta-amino alcohols.