Enantioselective lithiation/electrophile addition reactions with eight chiral Li-amide bases, 1 - 8, and five [Cr(arene)(CO)3] complexes, 9 - 13, were investigated. Restriction of conformational freedom in the chiral Li-amide base Li-1, in general, did not result in an increase in asymmetric induction. A new route to enantiomerically enriched (75 - 92%) planar chiral ortho-substituted benzaldehyde complexes via enantioselective lithiation of benzaldimine complexes 16 and 17 is reported. Within the (1S)-enantiomer series of o-substituted benzaldehyde complexes 18a - d, the sign of the specific rotation, [a], is found to be positive, except for the trimethylstannyl derivative 18b. This is interpreted in terms of a reversed conformation of the aldehyde group.