Cobalt-Catalyzed Enantioselective Synthesis of S-Stereogenic Sulfinamides Enabled by P-Stereogenic Phosphines with Aryl and Alkenyl Boronic Acids

Sulfur-stereogenic sulfinamides are not only key structures for biologically active molecules, ligands, and organocatalysts but also versatile intermediates to access a variety of organosulfur compounds containing S(IV) or S(VI) stereogenic centers. Despite progress in this field, catalytic enantioselective construction of sulfur-stereogenic centers remains a significant challenge. Herein, we present a cobalt-catalyzed protocol for catalytic enantioselective aryl and alkenyl addition to sulfinylamines with aryl and alkenyl boronic acids, affording a broad scope of sulfur-stereogenic sulfinamides with high efficiency and enantioselectivity. A phosphorus-stereogenic phosphinooxazoline ligand was developed, enabling the introduction of alkenyl groups onto the sulfur-stereogenic centers. Functionalization provided a variety of sulfur-stereogenic S(IV) and S(VI) compounds. Mechanistic studies and DFT calculations have been conducted to elucidate the reaction mechanism and the origin of enantioselectivity.