Abstract Efficient syntheses of (2R)-2-Boc-amino-3-phenylsulfonyl-l-propanol 3 and its enantiomer 9 from L-serine are described. The potential of these compounds in a novel general method for the synthesis of optically pure non protein α-amino acids in both the L and D configurations is exemplified by the preparation of N-Boc-L-and D- homophenylalanine,-norvaline and-norleucine.