Electricity‐Driven Radical Carbonyl Catalysis for Asymmetric Synthesis of <i>α</i> ‐Tertiary Amino Esters

Abstract

ABSTRACT Electrochemistry has become a powerful and environmentally sustainable tool for driving redox transformations in modern chemical synthesis. However, achieving stereocontrol in electrocatalysis remains a persistent challenge. Introducing asymmetric organocatalysis into electrosynthesis offers an attractive strategy for controlling enantioselectivity, though successful systems to date are very limited. This limitation largely stems from several key factors, including the highly polar electrochemical environment, which can weaken noncovalent interactions, and the transient, highly reactive nature of radical intermediates, both of which complicate enantiocontrol. Employing chiral pyridoxal as a catalyst, we have successfully developed a novel asymmetric electrocatalytic system. This system facilitates an electricity‐driven, asymmetric oxidative coupling of amino acid esters with silyl enol ethers through radical carbonyl catalysis. The method enables the efficient synthesis of biologically significant α‐tertiary amino acid esters with good yields and excellent stereoselectivities. Beyond efficiently activating the amino acid esters, the chiral pyridoxal catalyst also delivers exceptional enantiocontrol even under highly polar reaction conditions, establishing an efficient organocatalytic platform for asymmetric electrosynthesis.