钯、铑催化吲哚类化合物烃基化反应的机理和区域选择性的理论研究

Recently, the alkylation reactions of indole derivatives have received more and more attention in the fields of organic synthesis and catalysis. The C-H bond of indole derivatives could be activated and functionalized further catalyzed by rhodium and palladium. However, some problems, such as the preponderant mechanism in the reactions, the relationship between the reaction mechanism and conditions, and the origins of the regioselectivity, could not be solved still due to the many C-H bonds in the indole derivatives. In this project, by performing quantum chemistry methods, we will study the mechanisms in the alkylation reactions of indole derivatives catalyzed by rhodium and palladium, explore the impact of the directing groups and catalysts on the regioselectivity, and summarize the structure-function relationship between the regioselectivity and structure. On this basis, we expect to establish the mechanism models for the alkylation reactions of indole derivatives by using diazo compounds or organoboron as substrates. The research results of the project will expand the understanding to the alkylation reactions of indole derivatives, and supply the valuable information and theoretical guidance for the development of high-activity and high-selectivity catalysts and the optimization of the best experiment condition.

吲哚类化合物的烃基化反应已成为有机合成与催化反应领域的研究热点。研究发现，钯、铑可以有效地活化吲哚类化合物的C-H键并进一步实现官能团化。但由于吲哚类化合物可活化的C-H键较多，反应中究竟何种催化机理占主导地位，催化机理与反应条件的关系是什么，产生区域选择性的本质原因是什么，目前尚不明确。因此，本项目拟运用量子化学方法对钯、铑催化吲哚类化合物的烃基化反应的机理进行系统地理论研究，探究导向基团和催化剂对区域选择性的影响，总结出区域选择性与结构之间的构效关系理论。在此基础上，建立重氮化合物或有机硼作为烃基源时，吲哚类化合物烃基化的反应机理模型。项目的研究成果将有助于增强人们对吲哚类化合物烃基化反应的认识和理解，也将为高活性、高选择性催化剂的开发和反应条件的优化提供有价值的信息和理论依据。

应用量子化学方法，深入研究了钯、铑等过渡金属催化吲哚类及其它相关化合物的C-H和C-C活化反应的机理，分析了导向基团、催化剂和添加物等对反应中区域选择性的影响，总结出了区域选择性与结构之间的构效关系理论，完成了项目计划中规划的主要工作。项目的研究成果将有助于增强人们对吲哚类化合物烃基化反应的认识和理解，也将为高活性、高选择性催化剂的开发和反应条件的优化提供有价值的信息和理论依据。但是对于配体、添加物和溶剂等同时参与反应并影响选择性的机理尚需进一步研究。另外，我们研究了一些重要的有机催化反应，如：1）N-烷基-N-芳基邻氨基苯甲酸类物质的分子内环化的问题；2）Ni/Cu催化烯丙醇硅化反应的问题；3）质子型离子液体催化邻氨基苯甲腈和CO2合成喹唑啉的问题，等等。