Enantio- and Diastereoselective Synthesis of Axially Chiral Biaryl Sulfilimines via Cu/Co Anion Catalyzed Sulfur-Arylation of Sulfenamides

The enantio and diastereoselective synthesis of biaryl atropisomerism with a sulfur stereogenic center is a significant challenge for current chemical synthesis due to the lack of effective synthetic strategies. Herein, we report an efficient method for the construction of chiral biaryl sulfilimines possessing both axial and sulfur-central chiralities via copper/chiral cobalt anion catalyzed sulfur-arylation of sulfenamides with cyclic diaryliodonium salts under mild conditions, gaining various chiral sulfilimines in high yields (up to 99%) and excellent stereoselectivities (up to 98% ee, >20:1 dr). Moreover, the stereoselective sulfur-arylation was performed on a gram scale, and the corresponding products were transformed into various valuable chiral biaryl sulfoximine and their derivatives.