Enantioselective catalytic β-amination through proton-coupled electron transfer followed by stereocontrolled radical–radical coupling

-aryl carbamates are added to the β-position of α,β-unsaturated 2-acyl imidazoles using a visible light activated photoredox mediator in combination with a chiral-at-rhodium Lewis acid catalyst and a weak phosphate base, affording new C-N bonds in a highly enantioselective fashion with enantioselectivities reaching up to 99% ee and >99 : 1 dr for a menthol-derived carbamate. As an application, the straightforward synthesis of a chiral β-amino acid ester derivative is demonstrated.