FeCl3-Catalyzed Regio-Divergent Carbosulfenylation of Unactivated Alkenes: Construction of a Medium-Sized Ring.

A FeCl3-catalyzed regio-divergent carbosulfenylation of unactivated alkenes with electrophilic N-sulfenophthalimides has been developed. This protocol provides a straightforward and efficient access to various medium-sized rings, especially strained 7- and 8-membered carborings with a sulfur atom attached. The endo/exo selectivity in the reaction depends on the atom number of the chain between arene and alkene. Broad substrate scope, high yields, and gram-scale synthesis exemplified the utility and practicability of this protocol. In addition, this methodology can be extended to the carboselenylation of isolated alkenes.