In conclusion, we have developed an efficient and general method for enantioselective, silver-catalyzed intramolecular aziridination with carbamimidates that delivers excellent yields and stereoselectivities with broad scope. The reaction displays tolerance to diverse steric and electronic profiles as well as amenability to the large-scale synthesis. The enantioenriched bicyclic aziridines were versatile precursors for the regioand stereocontrolled syntheses of various 1,2-difunctionalized motifs. Future directions will focus on investigating further synthetic applications of these carbamimidate-derived products, as well as developing asymmetric silver-catalyzed NT protocols with other novel classes of nitrene precursors.