Nickel-catalyzed switchable asymmetric electrochemical functionalization of alkenes.

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.