Having established a broad functional group scope, we next explored substrate steric effects, beginning with matched and mismatched substrate catalyst pairings in the aziridination of L-citronellol derived alkenes. A stereogenic center at the gamma position relative to the alkene does not significantly impact the reaction, allowing both diastereomers to be accessed in high yields with excellent catalyst control for both the matched diastereomer (S,S)-29 (77%,97:3 d.r.) and the mismatched diastereomer (R,S)-29 (72%,7:93 d.r.). Moving the stereogenic center to the beta position reduces the yield of corresponding aziridines but does not impact the catalyst controlled diastereoselectivity in either the matched (R,S)-30 (30%,3:97 d.r.) or mismatched (S,S)-30 (24%,91:9 d.r.) catalyst substrate pairings. We note decreased yields, presumably due to steric effects, were also observed for allyl benzene which provided the aziridine 31 in a 18% yield 95:5 e.r. and vinyl cyclohexane providing aziridine 32 in a 14% yield (91:9 e.r.). The cis-aziridine 33 could be formed in a 61% yield, with a >20:1 d.r., and 86:14 e.r. from the corresponding Z-alkene, while the E-substituted alkene, as well as other more sterically challenging Z-substituted alkenes were found to be unreactive. Comparison of the chiral HPLC trace of 31 to standards of (R)-31 and (S)-31 prepared through intramolecular condensation of commercially available chiral amino alcohols allowed for the stereochemical assignment of (S) to 31 and other substrates by analogy.