Asymmetric electrocatalytic processes hold great promise for the sustainable synthesis
of chiral compounds. However, maintaining stereochemical control during the anodic
oxidative cross-dehydrogenative coupling of different nucleophiles poses significant
challenges. To address this, a novel electrocatalytic strategy has been developed
that achieves an enantioconvergent nitroalkylation between benzoxazolyl esters and
nitroalkanes via radical pathways. This method produces enantioenriched nitro esters
without the need for additional stoichiometric chemical oxidants. Mechanistic studies
have revealed that the nickel catalyst plays a critical role in both the electrochemical
activation and the determination of stereoselectivity. This approach facilitates transformations
that are challenging under thermal conditions, including umpolung reactivity, the
formation of quaternary carbon centers, and remote enantiocontrol.
Key words
electrocatalysis - radical reaction - nickel catalysis - enantioselectivity - cross-dehydrogenative
coupling - nitroalkylation
