Recently prepared layered double hydroxides (LDH)-supported OsO4, developed by the ion-exchange technique, was employed for catalytic asymmetric aminohydroxylation (AA) of olefins of varied nucleophilicity using Chloramine-T and (DHQ)(2)PHAL to afford chiral vicinal N-protected amino alcohols, important building blocks for many biologically active compounds and precursors for chiral ligands with moderate yields and ee's for the first time. Strong electron deficient olefins undergo AA reaction offering better yields than the less electron deficient and electron rich olefins due to the greater polarization of Os=NTs group in the former. The catalyst could be reused without any loss of enantioselectivity albeit a reduced activity. (C) 2002 Elsevier Science B.V. All rights reserved.