Enantioselective Electrocatalytic Nitroalkylation

Abstract

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

Publication History

Received: 08 January 2025

Accepted after revision: 07 February 2025

Accepted Manuscript online:
07 February 2025

Article published online:
19 March 2025

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