The halohydrocarbon-involved substitution reaction is one of the most classic transformations in organic chemistry for the formation of carbon-carbon and carbon-heteroatom bonds. With the utilization of halohydrocarbons such as aryl, alkenyl, and alkyl halides as reactants, a large number of optically active molecules have been constructed via SNAr, 5 SN1, or SN2 substitutions, or via couplings. Among these reactions, the catalytic asymmetric substitution reactions of readily available amino acid derivatives with halohydrocarbons provide a highly efficient pathway for the preparation of optically active unnatural disubstituted amino acids. However, in those reported methodologies, protection and deprotection manipulations are always unavoidable (Figure , path a). Notably, an ideal catalytic strategy leading to such products could directly promote the hydrocarbylation of N-unprotected amino acid esters with high efficiency (Figure , path b); however, such a valuable methodology has never been disclosed until now.