TBPO导向Cu(Ⅲ)催化吲哚C6位芳基化的机理研究  

Mechanism Study on TBPO-directed Cu(Ⅲ)-catalyzed C6-selective C-H Arylation of Indole

作　　者：耿翠环 郭尧[1] 陈鹏飞 李春洁 卢会杰 王博 GENG Cui-huan;GUO Yao;CHEN Peng-fei;LI Chun-jie;LU Hui-jie;WANG Bo(Anyang Institute of Technology,Henan Anyang 455000,China)

机构地区：[1]安阳工学院

出　　处：《广州化工》2019年第24期61-63,72,共4页GuangZhou Chemical Industry

基　　金：河南省高等学校重点科研项目(20B150001)

摘　　要：吲哚及其衍生物在新药开发和农药发展领域有着十分重要的作用。吲哚C-H活化顺序取决于吲哚本身的电子分布以及导向集团的影响。借助密度泛函理论详细研究了TBPO导向Cu(Ⅲ)催化吲哚芳基化的机理及导向基团作用。计算结果显示6号位芳香化吲哚是主要产物这与实验结果一致,证实了本文计算方法的可靠性。研究表明,C-H芳基化是经由碳-导向机理进行的,在该机理中,[Cu(Ⅲ)]基团由TBPO转移到了吲哚苯环上。本文的结果将为吲哚修饰体系提供理论指导。The indole scaffold plays an important role in the field of drug discovery and agrochemical development.The active sequence of indole C-H is relevant to the electron distribution character of indole when there is no directing group,otherwise,the position of C-H activation depends largely on the directing group.The mechanism and directing eect of the Cu(Ⅲ)-catalyzed site-selective C-H arylation of indole with TBPO acted as a directing group at the N position were investigated in details by means of DFT methods.It was suggested that the C6-selective arylation indole was the main product,which was consistent with the experimental results,which confirmed the reliability of the calculation method.The theoretical data indicated that the C-H arylation reactions followed a newly proposed C-directing mechanism,in which the Cu(Ⅲ)center transfered from O atom of TBPO to the C atom of indole benzene ring.These results provided key insights into the TBPO-directed Cu(Ⅲ)-catalyzed C6-selective C-H arylation of indole,and would facilitate the design of improved indole modification systems.

关 键 词：芳基化 铜催化 机理研究 

分 类 号：O643.3[理学—物理化学]