Enantioselective Synthesis of Axially Chiral Biaryl Sulfenamides via Cu-Catalyzed Sulfur-Arylation and Dealkylation

The enantioselective synthesis of axially chiral biaryl sulfenamides is a significant challenge for current chemical synthesis due to the lack of effective synthetic strategies. Herein, we report a one-pot two-stepwise process for the construction of chiral biaryl sulfenamides via copper/chiral cobalt anion catalyzed sulfur-arylation and dealkylation of cyclic diaryliodoniums under mild conditions. Various axial chiral biaryl sulfenamides were efficiently prepared in high yields (up to 95%) and enantioselectivities (up to 96% ee) which can be employed as novel axially chiral hypervalvent iodine catalyst for asymmetric catalysis, also they can be easily transformed into a wide range of valuable chiral biaryl sulfoximines and their derivatives.