A unified cobalt-electrocatalytic platform for enantio- and stereo-selective C–H and C–F functionalization of gem-difluoromethylene allenes

Abstract

While the merger of electrochemistry with enantioselective C–H functionalization has opened new avenues for assembling valuable chiral architectures, the simultaneous cleavage of strong C–H and C–F bonds via asymmetric electrocatalysis has remained elusive. Here, we present a unified electrochemical cobalt-catalyzed strategy that enables tandem enantioselective and stereoselective C–H and C–F functionalization with gem-difluoromethylene allenes, paired with hydrogen evolution. This resource-economic approach provides efficient access to a diverse range of enantiopure (Z)-fluoroalkenyl N-heterocycles bearing phosphorus-centered, axial, planar, and inherent chirality. Integrated experimental and computational mechanistic studies collectively support an unconventional Co(III/I/III/I) catalytic cycle, proceeding via sequential C(sp²)–H metalation, allene insertion, reductive elimination, C(sp³)–H metalation, alkene isomerization, and β–F elimination.