Catalytic Enantioselective Reductive Arylation and Alkenylation of Sulfinylamines to Access Sulfinamides Enabled by Cobalt Catalysis

Abstract This study reports a cobalt‐catalyzed method for the enantioselective reductive arylation and alkenylation of sulfinylamines, facilitating the efficient synthesis of enantiopure sulfinamides. By employing a cobalt/chiral diphosphine and tridentate ligand system, a range of diverse aryl and alkenyl iodides were successfully transformed into sulfinamides, achieving high yields and excellent enantioselectivity. This methodology underscores the utility of sulfinylamines as versatile electrophilic sulfur sources. Detailed mechanistic insights from density functional theory (DFT) calculations suggest that the key step involves migratory insertion into the sulfilimine group, which plays a crucial role in enantioselectivity. These findings offer a sustainable approach for the development of biologically relative enantiopure sulfur‐containing compounds.