Enantioselective Synthesis of Chiral Sulfinamidines via Asymmetric Amination of Sulfenamides Using a Chiral Phosphoric Acid Catalyst

Abstract Despite the significant applications of stereogenic‐at‐sulfur compounds in pharmaceutical sciences and organic chemistry, efficient methods for precise construction of valuable chiral sulfinamidines remain limited. Herein, we disclosed a chiral phosphoric acid‐catalyzed asymmetric strategy for the synthesis of chiral sulfinamidines through the direct amination of sulfenamides. This method demonstrated remarkable substrate scope and excellent yields and stereoselectivities across a diverse array of sulfinamidine compounds. The synthetic utility and practicability of this robust protocol were further highlighted through gram‐scale reactions, product derivatization and late‐stage functionalization of natural products and drugs.