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化学学报
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化学学报 ›› 1993, Vol. 51 ›› Issue (7): 713-719. 上一篇    下一篇

研究论文

有机磷化合物的研究 66.亚磷酸二酯对碳氮双键诱导不对称加成反应的分子力学研究

李树森;王国权;袁承业   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1993-07-15

Studies on organophosphorus compounds.pt. 6:A molecular mechanics study of the induced asymmetric addition of dialkyl phosphite to C=N double bond

LI SHUSEN;WANG GUOQUAN;YUAN CHENGYE   

  • Published:1993-07-15

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本文应有MNDO和MM2(85)研究了亚磷酸二酯对碳氮双键的诱导不对称加成反应的结构效应,催化剂种类和浓度以及溶剂等因素对诱导方向及de值的影响.结果表明,反应的诱导方向及诱导效果强烈地受到在反应过渡态中诱导基团的苯环与催化剂配合作用的影响.当苯环不参与配合时,诱导产物以R构型为主;当苯环参与配合时,诱导产物以S构型为主.该模型解释了催化剂种类和浓度、溶剂及酯烷基等结构效应.

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

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