项目名称： 钯催化C-H键活化构筑C-C键偶合反应机理的理论研究

项目编号： No.21501115

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 任颖

作者单位： 山西师范大学

项目金额： 22万元

中文摘要： 过渡金属钯催化C-H键的选择性官能团化反应已成为有机合成中构筑C-C键的重要策略。本项目将采用密度泛函理论方法，对Pd催化C-H键活化构筑C-C键烯基化、芳基化、炔基化及烷基化偶合反应的反应机理进行研究，重点阐明催化剂Pd(OAc)2在反应过程中催化机制。对一系列影响反应能垒的因素，包括溶剂效应、中性配体效应和金属中心效应进行理论研究。在此基础上，对反应底物中导向基的立体效应、电子效应和区域选择效应对反应活性和反应竞争选择性的影响将进行计算，揭示其对反应机制的作用，从而在底物的修饰和改变上实现产物的可调控性。理解催化剂的作用机制，对催化剂进行理论设计，改进催化剂对反应活性和选择性的影响。通过本项目的进行，将深化对Pd催化C-H键活化构筑C-C键偶合反应机制的认识，为发展新型高效催化剂提供理论指导。

中文关键词： 钯催化；密度泛函理论；反应机理；C-H键活化

英文摘要： Transition metal palladium-catalyzed direct selective C-H bonds functionalization has become an important strategy to form C-C bonds in organic synthesis. The purpose of this work is to clarify the detailed mechanism of Pd-catalyzed alkenylation, arylation, alkynylation and alkylation coupling reactions via C-H activation/C-C coupling, which use the density functional theory calculation. More importantly, the study aims to shed light on the catalytic mechanism of catalyst Pd(OAc)2 in the reaction. The various factors controlling the activation barrier will be discussed, which include the solvent effect, the neutral ligand effect, and the metal center effect. On the basis of the above results, the stereo effect, electronic effect, and regioselectivity of directing groups of the substrate will be investigated on the reactivity and the competition selectivity of the reaction, which can reveal the reaction mechanism and realize the control of the substrate by modifying and changing substrate. The catalyst will be theoretical designed on the basis of examination of catalytic reaction mechanism, which can improve the activity and selectivity of the catalyst in the reaction. Our project will increase the knowledge about the mechanism of Pd-catalyzed alkenylation coupling reaction and arylation coupling reaction via C-H activation/C-C coupling, and provide the theoretical guidance for the development of new, more powerful catalyst.

英文关键词： pd-catalyzed ;density functional theory ;reaction mechanism;C-H activation