We report a chiral-squaramide-catalyzed enantio- and diastereoselective synthesis of alpha-allyl amino esters. The optimized protocol provides access to N-carbamoyl-protected amino esters via nucleophilic allylation of readily accessible alpha-chloro glycinates. A variety of useful alpha-allyl amino esters were prepared, including crotylated products bearing vicinal stereocenters that are inaccessible through enolate alkylation, with high enantioselectivity (up to 97% cc) and diastereoselectivity (>10:1). The reactions display first-order kinetic dependence on both the alpha-chloro glycinate and the nucleophile, consistent with rate-limiting C-C bond formation. Computational analysis of the uncatalyzed reaction predicts an energetically inaccessible iminium intermediate, and a lower energy concerted S(N)2 mechanism.