No abstract

A simplified and appealing strategy via a chiral catalyst to facilitate the electrochemical process and provide asymmetric induction of radical reactions is particularly desirable and would have potential applications in electrosynthesis, organic chemistry, and drug discovery. Here, we introduced a novel electrolytic system that diverts the standard ionic reactivity to new catalytic functions, enabling mechanistically distinct single‐electron transfer‐based enantioselective routes to exhibit a brand‐new pattern of reactivity—electricity‐driven asymmetric catalysis as a privileged chiral platform for enantioselective radical allylation. The nickel‐catalyzed activation of nucleophiles triggered a single‐electron transfer process to provide a chiral catalyst‐bound radical cation intermediate, which could be applied as an alternative strategy for the development of stereocontrolled radical reactions.

The development of general electrocatalytic methods for the diversity-oriented regio- and stereoselective functionalization of alkenes remains a challenge in organic synthesis. We present a switchable electrocatalytic method based on anodic oxidative activation for the controlled liberation of chiral α-keto radical species toward stereoselective organic transformations. Electrogenerated α-keto radical species capture alkene partners, allowing switchable intermolecular alkene difunctionalization and alkenylation in a highly stereoselective manner. In addition to acting as proton donors to facilitate H 2 evolution at the cathode, the unique properties of alcohol additives play an important role in determining the distinct outcomes for alkene functionalization under electrocatalytic conditions.