This report describes the reaction of N-(thio)phosphoryl imines with diethylzinc under different conditions. An interesting and distinct chemoselectivity between hydrogen-addition and ethyl-addition to imine double bond is disclosed: in weakly polar solvent, e.g. toluene, N-(thio)phosphoryl imines were exclusively reduced in excellent yields via a β-H transfer from diethylzinc to imine double bond; in polar solvents like THF, the reduction product was competitively formed as a major product together with the minor product resulting from ethyl-addition to imine double bond; in sharp contrast, in the presence of strong coordinative additive N,N,N0,N0-tetramethylethylenediamine (TMEDA), the ethylation product was formed exclusively from the reaction of N-(thio)phosphoryl imine with diethylzinc. These results are discussed and explained in terms of the coordination interactions between the imine, solvent, and additive with diethylzinc.

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%.

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.

(1R,2R)-(—)-2-Dimethylamino-1-(4-nitrophenyl)-1,3-propanediol (2) was prepared starting from the readily available precursor of antibiotics chloramphenicol. The combination of compound 2 and L-proline have been found to be an efficient cocatalyst for the asymmetric Morita-Baylis-Hillman (MBH) reaction between methyl vinyl ketone (MVK) and aromatic aldehydes. The corresponding adducts were formed in reasonable chemical yields with good enantioselectivities (up to 82% ee). Performance of parallel cocatalytic reactions with chiral amine 2 and the two enantiomers of proline revealed that it is the proline stereochemistry that determines the configuration of the newly formed chiral center.

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%).