关键词: 量子化学, 有机磷化合物, 化学键, 结构效应, 亚磷酸酯类, 氨基膦酸, 分子力学, 不对称反应

The structural effect on the induced asym. addition of dialkyl phosphites to C:N double bond was investigated by MNDO and MM2 (85) calcns. As approximation, the structure of products was used as model of the transition state of the reaction. The influence of structure of dialkyl phosphites, the type and concentration of catalysts as well as the solvent effect on the induced direction and the d.e. values can be well rationalized by these calculation results. These data also reveal that the induced direction and the d.e. values are substantially governed by the formation of coordination species resulted from interactions between catalyst and the p electrons of benzene ring connected with asym. inductive substituents. If the catalyst is unable to coordinate with benzene nuclei, the principal product usually has R-configuration, otherwise, the S-configuration product will be predominant.

Key words: QUANTUM CHEMISTRY, ORGANO PHOSPHORUS COMPOUNDS, CHEMICAL BONDS, STRUCTURAL EFFECT, PHOSPHOROUS ACID ESTER, PHOSPHOAMIDIC ACID, MOLECULAR MECHANICS