Aziridination of N-sulfonyl imines with α-ketoesters in the presence of P(NMe2)3 is reported. Adducts derived from trivalent phosphorus reagents and α-ketoesters are effectively intercepted by imines, affording a range of aziridine-2-carboxylates. The diastereoselectivity of the reaction depends on steric hindrance from substituents on the substrates.