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.