A general methodology for the synthesis of 2-dialkylamino-1,1,2-triphenylethanol has been developed. Novel ligands 3, 4, and 5, bearing flexible alkyl chains on nitrogen have been synthesized by epoxide-ring opening of the encumbered (S)-triphenyl-oxirane. These ligands along with 2-piperidino-1,1,2-triphenyl ethanol 1 have been tested in the addition of dimethylzinc to alde-hydes. This allowed for the assessment of the structural features that favor the catalytic activity and selectivity of the ligands with respect to nitrogen substitution.