CuI催化溴代苯与L-缬氨酸的反应机理的研究  

Theoretical Investigation on the Reaction Mechanism of Aryl Halides with α-amino Acids Catalyzed by CuI

作　　者：潘晓晓[1] 邹良明[2] 岳文喜[2] 李来才[1] 

机构地区：[1]四川师范大学化学与材料科学学院,四川成都610066 [2]四川工商职业技术学院,四川都江堰611837

出　　处：《四川师范大学学报（自然科学版）》2014年第2期228-234,共7页Journal of Sichuan Normal University（Natural Science）

基　　金：四川省教育厅自然科学重点基金(13ZA0150)资助项目

摘　　要：采用密度泛函理论研究了CuI催化溴代苯与L-缬氨酸发生C—N交叉偶联反应的微观反应历程.在B3LYP/6-311+G*水平上对反应过程中所有反应物、过渡态、中间体以及产物的几何构型进行了优化,通过能量和振动分析确认了过渡态的真实性;并且在相同基组水平上应用自然键轨道(NBO)和分子中的原子理论(AIM)分析了这些化合物的成键特征和轨道间的相互作用.研究发现了2条可能的反应通道IA与IB,其控制步骤活化能分别为282.2和219.2 kJ/mol,由以上比较结果可以看出,IB通道具有较低的活化能,即IB通道为整个反应的最优反应通道,并且IB反应通道中,CuI、CuCl催化反应活化能依次升高;这些都与实验结果一致.The reaction mechanism of copper-catalyzed C--N coupling reaction of aryl halides with a-amino acids was studied using the density functional theory at B3LYP/6-311 ＋ G ＊ level. The geometric configurations of reactants, intermediates, transition states and products were optimized. Nature bond orbital （NBO） and atoms in molecules （AIM） theories were used to discuss the bond- ing nature and orbital interactions at the same levels. Two possible reaction pathways, IA and IB, were investigated and their activation energies of the limiting steps are 282.2 and 219.2 kJ/mol, respectively. From the above results, it can be seen that the IB channel has lower activation energy. IB channel is thus the main reaction channel in the whole reaction. The activation energy of limiting steps cata- lyzed by CuI has lower activation energy than that by CuC1. The above findings are in agreement with the experimental results.

关 键 词：L-缬氨酸 溴代苯 偶联 Cu催化 过渡态 反应机理 

分 类 号：O641.121[理学—物理化学]