In the presence of an effective air-stable nucleophilic trialkylphosphane orgaocatalyst, 1,3,5-triaza-7-phosphaadamantane, N-diethoxythiophosphorylimines 1 and N-diphenylthiophosphinoylimines 2 exhibited good reactivity in the methyl vinyl ketone or methyl acrylate based aza-Morita–Baylis–Hillman reaction. The corresponding products were obtained in fair-to-excellent chemical yields. Moreover, the chiral-imine-induced diastereoselective aza-MBH reaction was also realized with 90% de. This reaction provides a convenient method for the synthesis of synthetically valuable α-methylene-β-amino ketone or acid derivatives.

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.

Some new chiral cyclic o-hydroxylarylphosphonodiamides were synthesized from (−)-α-phenylethylamine and found to be efficient ligands for the Ti(OPr-i )4 catalyzed asymmetric trimethylsilylcyanation of aromatic aldehydes. Corresponding cyanohydrins were obtained in good chemical yield and enantiomeric excesses up to 90%.

Some new chiral bifunctional o-hydroxyarylphosphonodiamides were synthesized starting from (+)-cis-1,2,2-trimethylcyclopentane-1,3-diamine and the absolute configuration of the phosphorus atom was determined by X-ray diffraction analysis. Excellent enantioselectivity (up to 98% ee) was achieved in asymmetric silylcyanation of aromatic aldehydes using a chiral titanium complex formed in situ from Ti(OiPr)4 and o-hydroxyarylphosphonodiamide as the catalyst.

α-Disubstituted pyrrolidine-2-methanols were synthesized starting from L-proline and their application as chiral auxiliary in the asymmetric NaBH4 reduction of α,β-unsaturated triazolyl ketones was investigated. The corresponding α,β-unsaturated triazolyl alcohol derivatives (Uniconazole and Diniconazole) were obtained in good chemical yields with high ee values (up to 93%).