ortho-Substituted [Cr(CO)₃(benzaldehyde)] complexes are obtained via nucleophilic addition of alkyl- and aryllithium reagents to a [Cr(CO)₃(phenylmethaneimine)] complex followed by endo-hydride abstraction with triphenylmethyl cation. This sequence, when carried out with a [Cr(CO)₃(benzaldehyde SAMP hydrazone)] complex affords substituted derivatives (Me, Bu, Ph, vinyl) with high (≥97%) diastereoselectivity and, after hydrolysis, ortho-substituted [Cr(CO)₃(benzaldehyde)]((S)-1) complexes of high enantiomeric purity.