We began our investigation by exploring the effect of indenyl ligand electronics on catalyst reactivity in the aziridination of 1-nonene (3) to form aziridine (R)-4. We selected our previously developed planar chiral catalyst 2 as well as four electronically tuned variants 5-8 (Figure ). Catalysts 5-8 are accessible in two steps via racemic Rh(I)(COD) intermediates which can be separated via chiral preparative HPLC to afford enantiopure catalysts (see Supporting Information for details). Subjecting 3 to the conditions previously reported by Rovis in the presence of CF3 substituted catalyst (S,S)-5 (2.5 mol%) provided the aziridine (R)-4 in 13% with excellent enantioselectivity (96:4 e.r.) (Figure ). Using methoxy substituted catalyst (S,S)-6 improved the yield of (R)-4 to 23% while maintaining excellent enantioselectivity (96:4 e.r.). We believe the out of plane orientation of the phenyl moiety prevents the methoxy substituent from donating electron density to the indene via resonance and it functions as an electron withdrawing group through inductive effects. Catalyst (S,S)-2 further improved the yield of (R)-4 to 27% while still achieving high enantioselectivity (93:7 e.r.). Using the more electron rich catalyst (S,S)-7 improved the yield of (R)-4 to 37% (95:5 e.r.). A further increase in yield was achieved when the permethylated catalyst (S,S)-8 was used providing (R)-4 in a 44% yield with the same excellent enantioselectivity (95:5 e.r.). To capitalize on this reactivity trend, we designed a more electron rich catalyst (±)-9 which significantly improved the yield of 4 to 77% (Figure ). Unfortunately, (±)-9 could only be accessed in its Scheme 1. Functionalization of Activated and Unactivated Alkenes racemic form as design elements which made this catalyst so effective, prevented separation of the planar chiral Rh(I) intermediate whether through chiral preparative HPLC, or other planar chiral catalyst resolution strategies. We note that in these initial conditions, no halide abstracting additive, commonly required when using this family of catalyst was included. We therefore hypothesize that this trend in catalyst reactivity could stem from the electron donating catalyst's 7-9 ability to better facilitate the dissociation of the iodide ligands by stabilizing the resulting cationic Rh(III) species.