Enantioselective Inter- and Intramolecular Sulfenofunctionalization of Unactivated Cyclic and (Z)‑Alkenes

A method for the enantioselective, Lewis base-catalyzed sulfenofunctionalization of cyclic and (Z)-alkenes is reported. The intermediate thiiranium ion generated in the presence of a selenophosphoramide catalyst is intercepted by a variety of nucleophiles. A diverse array of inter- and intramolecular functionalizations proceed in high yield and good to high enantioselectivity (86:14–98:2 er). Prior experimental and computational studies indicated such enantiotopic face discrimination to be poor; however, the results disclosed herein remediate the previous findings. Control experiments were performed to investigate the different behavior of (Z)-alkenes and their more established (E)-counterparts.