Quantitative Evaluation of Reaction Paths and Its Application for the Prediction and the Design of Reactions.

反应路径的定量评估及其在反应预测和设计中的应用。

基本信息

批准号：
02303004
负责人：
HIROTA Minoru
金额：
$ 8.32万
依托单位：
Faculty of Engineering, Yokohama National University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Co-operative Research (A)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1992
项目状态：
已结题

项目摘要

This co-operative research has been carried out by organizing four subbgroups. (1)Electronic Aspects of Reaction mechanism and Path The reaction paths of the cyclization of penta-1,4-dienes and the additions to fullerene were elucidated theoretically by ab initio MO calculations. On the other hand, the resonance demands in the solvolysis of benzyl derivatives were analyzed very exactly and correlated to its mechanism. Molecular interactions involved in the organic reaction mechanism were studied both from theoretical and kinetical points of view.(2)Steric Course and Stereoselectivity of Reactions By use of molecular mechanics, steric hindrance was evaluated quantitatively and the steric course of the reactions of trishomocubanes was estimated. The sterically congested reaction field was desigened in STECAR concept and in the BINAP-RU hydrogenation.(3)Structures and Interactions in Reaction Intermediates The structures and properties of stable cations, such as alpha-arylvinyl cation and bicyclic alpha-keto-cations, and polyradicals were elucidated. In contrast, very fast electron transfer rection and very short-lived photo-excited states were identified by laser photolysis and other new techniques. Sonochemical method was applied to the switching of reactions.(4)Reactions of Heteroatom-Cntaining and Biological Molecules Silicenium ions, polysilacyclo- alkynes, hypervalent compounds, chiral bismuthines, [3,3]metacylophanes, and other novel compounds were designed and their applications were pursued. On the other hand, reaction mechanisms of model enzymes were studied kinetically.

这项合作研究是通过组织四个子组进行的。（1）反应机理和路径的电子方面通过从头开始计算，理论上阐明了PENTA-1,4-二烯环化的反应路径和富勒烯的添加。另一方面，对苄基衍生物的溶解度的共振需求非常准确地分析并与其机理相关。从理论和动力学的角度研究了参与有机反应机制的分子相互作用。（2）通过使用分子力学，定量评估了反应的空间过程和反应的立体选择性，并估算了三丝体群体反应的空间。（3）反应中间的结构和相互作用在稳定阳离子的结构和特性（例如α-芳基烯基阳离子）和二维甲基二酮甲酸和polardadicals中均具有稳定阳离子的结构和特性。相比之下，通过激光光解和其他新技术鉴定出非常快速的电子传递折磨和非常短的光兴奋状态。（4）杂原子含量和生物分子硅离子，多乙醇酸性，高价值化合物，手性bismuthines，[3,3] Metacylanes以及其他新颖的化合物的应用以及其应用。另一方面，对模型酶的反应机制进行了动力学研究。