The reaction of optically active 3-alkyl-2-vinylaziridines with various aldehydes in the presence of InI and Pd(PPh3)(4) gives rise to chiral syn,syn-2-vinyl-1,3-amino alcohols possessing three contiguous chiral centers stereoselectively. The ratio of the syn,syn-isomer to the other three isomers is significantly affected by the C3-substituents of aziridines as well as the alkyl groups of aldehydes. In addition, the obtained 1,3-aminoalcohols can be converted into biologically important p(2,3)-amino acid derivatives. (C) 2002 Elsevier Science Ltd. All rights reserved.