过渡金属（Au，Pt，Pd）2.0多靶点高效催化活化端炔基化合物C(sp3)-H键构建C-C键反应的理论研究

过渡金属2.0多靶点高效催化端炔基化合物C(sp3)-H键构建C-C键是有机化学研究中具有战略意义的前沿。目前，该类反应的研究虽然在实验上取得了重要成果，但其机理研究还很缺乏。本项目以理论化学为基础，利用密度泛函理论等方法，对过渡金属（Au，Pt，Pd）等2.0多靶点高效催化活化端炔基化合物C(sp3)-H构建C-C键的反应进行系统而深入的理论研究，以期解决该类反应在催化机理方面的关键科学问题。从催化剂金属中心、配体配位环境、催化剂特征位点的取代、底物不同位点的化学环境这四个最可能影响C(sp3)-H活化催化反应的因素出发，考察多靶点进攻/作用方式、催化反应活性中间体、反应活性、反应势能面、反应选择性（化学、区域、立体及对映选择性）以及它们彼此之间的内在关系和规律等关键理论问题，从而为改进已有的多靶点高效催化体系，有效预测和指导设计新的催化剂和新的多靶点催化反应体系提供思路。

The theoretical calculation methods are of the most valuable approaches using to investigate the mechanism of the reaction which is catalyzed by transition-metal. Efficient catalysis C(sp3)-H of diyne systems with multi-target of transition metal catalyst forming the C-C bonds has been the subject of many studies in recent five years for the more atom-economical and environment-friendly reasons which is within today’s highly sensitive issue of sustainable chemistry. However, there still exist some critical lacks of systematic research on them. In present project, all analysis and discussion are on the basis of four most possible factors involving in determining mechanism and selectivity using the computational methods: (a) the metal center; (b) the ligand effect; (c) the substitute on the catalysts; (d) the substitute on the substrates. We try to investigate the active species, the reaction reactivity, the reaction pathway, the potential-energy surfaces, the manner of C(sp3)-H bond activation, the chemo-, regio-, stereo- and enantioselectivity, and the relationship the mechanism and selectivity. These fundamental guidelines would help advance the development of efficient and structurally favorable transition-metal catalysts for C(sp3)-H catalyzed forming C-C bond.