Arene cyclopropanation offers a direct route to higher-order, non-aromatic carbocycles; however, the inherent issue of dictating site selectivity has cumbered the development of novel intermolecular reactions that directly engage the arene pool. This paper describes a highly regio- and stereoselective, Rh2[(S)-PTTL]4-catalyzed arene cyclopropanation using α-cyanodiazoacetates to afford stable norcaradienes bearing three stereogenic centers, one of which is an all-carbon quaternary center. The enantioenriched norcaradienes served as tunable templates for further transformation into stereochemically dense, fused and bicyclic carbocycles containing transmutable functionality.