We recognized the possibility of developing a broadly applicable asymmetric unactivated alkene aziridination method building from a report by Rovis and co-authors for the synthesis of pyrrolidines from unactivated terminal alkenes (Scheme 1b, top). Therein, the use of [Ind*RhCl2]2 in combination with a hydroxylamine nitrogen transfer reagent 1 and TfOH allowed for formal [4+1] cycloadditions. During their investigation, they determined that the transformation proceeded via an isolatable aziridine intermediate demonstrating a previously unprecedent mode of reactivity for a Rh(III) catalyst. Additionally, they noted that the indenyl ligand was critical for reactivity, with the analogous [Cp*RhCl2]2 catalyst resulting in significantly reduced yields. Inspired by this precedent, we sought to render the aziridination enantioselective through the use of our planar chiral Rh(III) indenyl catalyst 2, developed in the context of an enantioselective allylic C-H amidation reaction (Scheme 1b, bottom). Herein we report the development of enantioselective aziridination method targeting unactivated alkenes using a simple hydroxylamine in combination with a planar chiral Rh(III) indenyl catalyst (Scheme 1c). Furthermore, we detail our computational investigations into the mechanism of this reaction.