A novel enantioselective aziridination method for unactivated terminal alkenes is reported using a planar chiral rhodium(III) indenyl catalyst. This method enables the efficient synthesis of enantioenriched chiral aziridines with high functional group tolerance and chemoselectivity. The reaction proceeds through a stepwise mechanism involving alkene migratory insertion, forming a strained four-membered metallacycle, which is both enantio- and rate-determining. Computational studies reveal that the reaction mechanism involves the formation of an amide intermediate, followed by nitrene formation and subsequent aziridine formation. The enantioselectivity arises from steric interactions between the substrate, the sulfonamide, and the phenyl substituent on the catalyst's indenyl ligand. The catalyst's planar chirality and the specific electronic properties of the indenyl ligand are critical for achieving high enantioselectivity. The method demonstrates broad substrate scope, including various functional groups and heterocycles, and is applicable to both activated and unactivated alkenes. The reaction conditions are mild, and the catalyst is easily prepared, making it a versatile and efficient approach for the synthesis of chiral aziridines.A novel enantioselective aziridination method for unactivated terminal alkenes is reported using a planar chiral rhodium(III) indenyl catalyst. This method enables the efficient synthesis of enantioenriched chiral aziridines with high functional group tolerance and chemoselectivity. The reaction proceeds through a stepwise mechanism involving alkene migratory insertion, forming a strained four-membered metallacycle, which is both enantio- and rate-determining. Computational studies reveal that the reaction mechanism involves the formation of an amide intermediate, followed by nitrene formation and subsequent aziridine formation. The enantioselectivity arises from steric interactions between the substrate, the sulfonamide, and the phenyl substituent on the catalyst's indenyl ligand. The catalyst's planar chirality and the specific electronic properties of the indenyl ligand are critical for achieving high enantioselectivity. The method demonstrates broad substrate scope, including various functional groups and heterocycles, and is applicable to both activated and unactivated alkenes. The reaction conditions are mild, and the catalyst is easily prepared, making it a versatile and efficient approach for the synthesis of chiral aziridines.