Rh 2 esp 2 were used (up to 99% ee), albeit with a significant decline in ee employing (Z)-olefins. Later that year, our group reported asymmetric silver-catalyzed NT of homoallylic carbamates bearing unconjugated, Z/E di-/trisubstituted olefins to give aziridines in a range of ee values depending on substrate. Given the scarcity of asymmetric intramolecular aziridination methods, we were interested in opportunities to further improve the scope and utility of silver-catalyzed asymmetric aziridination via NT. Carbamimidates are an underexplored class of nitrene precursors, where the additional valency on the imidate nitrogen, as compared to carbamates or sulfamates, offers an opportunity to tune catalyst/substrate interactions in the NT transition state to improve chemo-, site-and enantioselectivity. In addition, the 5-member dihydrooxazol-2-amine and 6-member 1,3-oxazin-2-amine products from asymmetric aziridination and ring-opening sequences employing carbamimidate precursors are found in several compounds with useful bioactivities (Figure ). Despite their structural resemblance to carbamates, thus far only one example of the use of carbamimidates has been reported. The Dauban group employed Rh-catalyzed intramolecular C-H aminations of carbamimidates (Scheme 1C) to give racemic products. Prompted by this example and reports on promising applications of cyclic carbamimidates in medicinal chemistry, we herein disclose a method for asymmetric intramolecular aziridinations of homoallylic carbamimidates mediated by a chiral silver-BOX complex (Scheme 1D). We envisioned that the extra bulk from the imine N-protecting group in carbamimidates, as compared to carbamates, would have a substantial impact on catalyst-substrate steric interactions that could lead to increased levels of chemo-and enantioselectivity with suitable catalysts.