The reaction of meso-(2, 4-hexadien-1, 6-dial)Fe(CO) 3 complex 1 with several alkylzincs in the presence of 50 mol% of(S)-(+)-diphenyl(1-methylpyrrolidin-2-yl)methanol 6a proceeded with high enantiotopic group- and diastereotopic face-selectivity to give(2R, 6S)-alcohol complexes 2a-c as major products, except in the case with dimethylzinc (>90% de and >98% ee). On the other hand, the methylation of 1 with Me 2Zn proceeded with high enantioselectivity by adding 1.8 equiv. ofTi(Oi-Pr) 4 in the presence of 3 mol% of(S, S)-1, 2-bis(trifluoromethylsulfonamide)cyclohexane 9a (82% de, 96% ee). The enantioselective alkylation was also applied to the kinetic resolution of racemic (sorbic aldehyde)Fe(CO) 3 complex 10. [Display omitted]