Directed Evolution of Nonheme Fe Enzymes for Enantioselective and Regiodivergent 1,3- and 1,4-Nitrogen Migration: Biocatalytic Asymmetric Synthesis of Noncanonical α- and β-Amino Acids

exhibited similar kinetic isotope effects for both 1,5- and 1,6-HAT pathways, suggesting that enzyme engineering controls regio- and enantioselectivity but does not alter the intrinsic transition-state properties of the HAT event. Together, these results further established engineered nonheme Fe enzymes as an excellent platform for the development of stereoselective, synthetically useful non-native biocatalytic transformations.