Whereas treatment of the allylic mesylates of N-protected 2-alkyl-4-amino-(E)-2-alken-1-ols with sodium hydride in DMF yields exclusively the corresponding thermodynamically less stable 2,3-trans-2-alkenyl-3-alkylaziridines, exposure of the methyl carbonates of N-protected 2-alkyl-4-amino-(E)-2-alken-1-ols to a catalytic amount of Pd(PPh(3))(4) in THF or 1,4-dioxane affords predominantly the corresponding thermodynamically more stable 2,3-cis-2-alkenyl-3-alkylaziridines. The kinetically favored trans-selective aziridination would be attributed to the allylic 1,3-strain in aza-anionic intermediates. The conformational analysis of the sterically highly congested 2-alkenylaziridines thus obtained is also presented.