Chemistry

Organocatalysis

Electrophile

Oxidative phosphorylation

Catalysis

Nucleophile

Organic chemistry

Combinatorial chemistry

Iminium

Enantioselective synthesis

Enamine

Biochemistry

Oxidative coupling of methane

ACS Catalysis

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.

Catalytic Asymmetric Oxidative Enamine Transformations