Chiral Lewis Base/Achiral Acid Co‐Catalyzed Atroposelective Sulfenylation of Pyrrole Derivatives: Construction of C—N Axially Chiral Sulfides

Comprehensive Summary Chiral BINAM‐derived selenide/achiral acid co‐catalyzed atroposelective electrophilic sulfenylation of pyrrole derivatives has been realized for the first time. A variety of C—N axially chiral sulfur‐containing pyrrole derivatives were readily obtained in moderate to good yields with moderate to excellent enantioselectivities. This catalytic system involves sequential desymmetrization and kinetic resolution. Chiral BINAM‐derived selenide/achiral acid co‐catalyzed atroposelective electrophilic sulfenylation of pyrrole derivatives has been realized for the first time.