Enamine catalysis is a prevalent strategy for the functionalization of aldehydes/ketones with electrophiles. Recently, the advent and development of oxidative enamine catalysis have allowed for the coupling of enamines with readily available nucleophiles under oxidative conditions, significantly expanding the domain of typical enamine catalysis. In this perspective, we summarize the recent advances in asymmetric oxidative enamine catalysis. On the basis of the oxidative strategy, these could be classified as (1) oxidation of nucleophile, (2) oxidation of enamine via single-electron transfer (SOMO catalysis), and (3) oxidation of enamine to α,β-unsaturated iminium ion, i.e. oxidative iminium catalysis. These strategies have enabled efficient oxidative functionalizations of aldehydes/ketones with various O-, N-, and C-centered nucleophiles in a highly stereocontrolled manner.

We report herein a direct unsymmetric coupling and controllable aromatization reaction of saturated N-heterocycles enabled by synergistic photoredox and acid catalysis. The reaction furnishes C2−C3 connected biheterocycles in a highly chemo-and regioselective manner under rather mild conditions. Mechanistic studies indicated that the reaction proceeded via enamine-iminium coupling leading to exclusively C2−C3 connection.

We report herein an asymmetric C–H dehydrogenative allylic alkylation by a synergistic catalytic system involving a chiral primary amine, a photoredox catalyst, and a cobaloxime cocatalyst. The ternary catalytic system enables the coupling of β-ketocarbonyls and olefins with good yields and high enantioselectivities. Mechanism studies disclosed a cooperative radical addition process with a chiral α-imino radical and Co­(II)-metalloradical wherein the chiral primary aminocatalyst and the cobaloxime catalyst work in concert to control the stereoinduction.