The enantioselective aldol reaction of glycinates with aldehydes — a direct entry to an important class of noncanonical amino acids — has so far eluded small-molecule catalysis. Now, mimicking the cofactor of threonine aldolase enzymes, a chiral carbonyl catalyst that is remarkably effective for this reaction has been developed. This asymmetric protocol has been successfully applied to more than a thousand aldehyde substrates.