Electrocatalytic Enantioselective Reductive Cross-Coupling for Accessing Chiral α-Aryl Phosphonates.

Electrochemical asymmetric catalysis has emerged as a promising and sustainable strategy for the synthesis of chiral molecules. The present study draws inspiration from the synergistic potential inherent in the merging of electrochemistry with nickel catalysis, which establishes a practical and versatile platform for asymmetric C-C bond formation in synthetic chemistry. This report details an electrochemically driven, nickel-catalyzed enantioselective reductive cross-coupling of α-bromophosphonates with aryl iodides. This method delivers enantioenriched α-aryl phosphonates in excellent enantioselectivity under mild conditions, which exhibits a broad substrate scope, high functional-group tolerance, and exceptional stereocontrol, as demonstrated through the late-stage functionalization of bioactive molecules. Mechanistic studies, incorporating cyclic voltammetry and control experiments, have indicated that a NiI species activates the α-bromophosphonate via single-electron transfer.