Herein we describe the application of a series of newly developed Ru-chloramphenicol base derivative complexes as catalysts for the highly diastereo- and enantioselective transfer hydrogenation of N-Boc α-amino-β-ketoesters for the asymmetric synthesis of anti-N-Boc-β-hydroxy-α-amino esters. This report highlights the utility of this catalytic methodology for the preparation of pharmaceutical compounds bearing a N-Boc α-amino-β-hydroxy substructure with two stereocenters.