A chiral benzodiazepine derivative 1 was synthesized starting from o-nitrobenzoyl chloride and methyl L-prolinate hydrochloride. Diastereomeric (1R,2R,1’S)-(+)-2-[N-methyl-N-(α-phenylethyl)amino]cyclohexanol 3a and (1S,2S,1’S)-(+)-2-[N-methyl-N-(α-phenylethyl)amino]cyclohexanol 3b were synthesized starting from (S)-α-phenylethylamine and cyclohexene oxide via ringopening, diastereomer separation and N-methylation. (S,S)-octahydrodipyrrolo[1,2-a:1’,2’-d]pyrazin 5 was synthesized from methyl L-prolinate. Chiral tertiary amines 1, 3a, 3b and 5 almost cannot catalyze the Baylis–Hillman reaction between o-nitrobenzaldehyde and methyl vinyl ketone (MVK). However, they functioned as efficient catalysts for this reaction in the presence of L-proline. The corresponding adducts were obtained in good yields with enantioselectivity of 83% ee, 81% ee, 51% ee and 66% ee, respectively.