几类重要有机化学反应的机理研究

本项目拟对几类重要的有机化学反应的机理进行研究，希望能从分子层次对这些反应的详细过程以及这些反应的热力学,动力学,反应决速步,反应立体和位置选择性等进行研究. 本项目所选择的几类重要的有机化学反应包括:（1）过渡金属催化的环加成反应；（2）金属卡宾参与的碳-碳键和碳-杂原子键的形成反应，共轭双烯导向的碳氢键活化反应；(3) 金属催化的1,n-烯炔骨架环化重排反应；（4）金属催化的氧气参与的脱氢反应与加氧反应；（5）有机小分子催化的三氯氢硅还原亚胺的不对称反应. 该研究将主要利用计算化学，辅以实验技术手段研究这些反应的反应机理,实现对以上反应机理的系统性认识和积累. 同时该研究还希望能从这些机理研究的基础上设计一些新的反应和催化剂, 并通过计算和实验来研究它们的可行性。

This research project mainly focuses on mechanistic investigations of several important organic reactions. It aims at in-depth understandings of the details of how these reaction occur at the molecular level, what are these reactions' thermodynamics, kinetics, rate-determining stesp, stereochemistry, regiochemistry, et al. The important organic reactions that we would like to study include: (1) Transition metal-catalyzed cycloaddition reactions; (2) Metal-carbene mediated C-C bond and C-X bond formations, Diene-assisted C-H activation; (3) Metal-catalyzed 1,n-eneyne rearrangements;(4)Metal-catalyzed areobic dehydrogenation and oxygenation addition;(5)Organocatalyst-catalyzed asymmetric imine reduction by HSiCl3. Through combining computational chemistry and experiments, our mechanistic studies will provide insights to understand the reaction mechanisms systematically. Also based on the mechanistic studies, new reactions and new catalysts will be designed and tested computationally and experimentally.