The reaction of (S)-triphenylethylene oxide (3) with diisopropoxytitanium(IV) diazide in benzene solution at 70 °C takes place readily in a completely regioselective and stereospecific manner to afford (S)-2-azido-1,2,2-triphenylethanol (6). Reduction of the azide by catalytic hydrogenation leads to (S)-2-amino-1,2,2-triphenylethanol (5) that, by N,N-dialkylation with 1,4-dibromobutane, 1,5-dibromopentane, 1,5-dibromo-3-oxapentane, α,α‘-dibromo-o-xylene, and methyl iodide, affords the corresponding (S)-2-dialkylamino-1,2,2-triphenylethanols (7a−e). On the other hand, the reaction of 5 with benzyl bromide or 1-iodobutane takes place as a monoalkylation, leading to the corresponding (S)-2-alkylamino-1,2,2-triphenylethanols (8f,g). The performance of amino alcohols 7a−e as ligands for the catalytic enantioselective addition of diethylzinc to benzaldehyde has been studied, with enantioselectivities of 94−97% being recorded. The best performing ligands in this family, 7a [(S)-1,2,2-triphenyl-2-(1-pyrrolidinyl)...