Direct enantioselective synthesis of (R)- and (S)-N-Cbz- or N-BOC-protected alpha-arylglycinols from styrenes via catalytic asymmetric aminohydroxylation, with enantioselectivities up to 99% and isolated yields up to 80%, is described. In a subsequent oxidation step, these glycinols yield the corresponding carbamate-protected alpha-arylglycines.