Chiral anionic ProPhenol ligand enabled nickel catalyzed enantioselective synthesis of sulfinamides

Anionic ligands capable of forming covalent bonds with metal centers serve as a powerful tool for precisely modulating the stereoelectronic properties of catalysts. However, the development and application of chiral anionic ligands in transition metal-catalyzed asymmetric synthesis remain underexplored. Here, we report a chiral anionic ProPhenol ligand, which effectively facilitates the nickel-catalyzed asymmetric synthesis of chiral (hetero)aryl and alkenyl sulfinamides under mild reaction conditions. Remarkably, this catalytic system exhibits exceptional efficiency, achieving high yields and stereoselectivity control with only 0.5 mol% catalyst loading in 5 mmol-scale reactions, underscoring its practical synthetic utility. Comprehensive density functional theory (DFT) calculations reveal that the oxygen-boron interaction between the ligand and substrate plays a critical role in facilitating the transmetalation process, while hydrogen-bonding interactions between the ligand and trityl sulfinylamine (TrNSO) significantly enhance enantioselectivity in this transformation.