A facile and highly enantioselective approach towards 2-substituted 3-bromopyrrolidines has been developed. The process involves an amino-thiocarbamate catalyzed bromoaminocyclization of 1, 2-disubstituted olefinic amides. The pyrrolidine products could readily be converted into other useful building blocks including a dihydropyrrole and a 2- substituted pyrrolidine.