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.