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  

Studies on Organophosphorus Compounds 66. A Molecular Mechanics Study of the Induced Asymmetric Addition of Dialkyl Phosphite to C=N Double Bond

作　　者：李树森[1] 王国权[1] 袁承业[1] 

机构地区：[1]中国科学院上海有机化学研究所,上海200032

出　　处：《化学学报》1993年第7期713-719,共7页Acta Chimica Sinica

基　　金：国家自然科学基金;中国科学院计算机化学开放实验室资助的课题

摘　　要：本文应用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.The structural effect on the induced asymmetric addition of dialkyl phosphites to C=N double bond was investigated by MNDO and MM2 (85) calculations. As appro ximation, 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 de values are substantially governed by the formation of coordination species resulted from interactions between catalyst and the π electrons of benzene ring connected with asymmetric inductive substituents. If the catalyst ia unable to coordinate with benzene nuclei, the principal product usually has R-configu ration, otherwise, the S-configuration product will be predominant.

关 键 词：不对称加成 碳氮双键 有机磷化合物 

分 类 号：O627.51[理学—有机化学]