利用金属氮宾高效引发选择性C-H键插入进行不对称合成C-N键的反应对有机合成具有战略意义，适应催化反应对高效、高选择性、绿色环保和"原子经济性"的要求，是有机化学研究的热点。但高效金属氮宾生成机理和高选择性（化学、区域、对映和立体）因素还不清楚。本项目以理论化学为基础，利用密度泛函理论、从头算方法以及QM/QM(MM) 方法，对金属氮宾高效引发选择性C-H键插入不对称合成C-N键的反应进行系统而深入的理论研究。从影响C-H胺化反应的四个最可能因素（金属中心、配体效应、氮宾N上取代基效应、底物C-H键取代基效应）出发，考察活性中间体、反应活性、多态势能面、C-H进攻氮宾的方式、化学与区域选择性、立体和对映选择性以及它们的内在关系和规律等关键理论问题。从而为改进已有的金属氮宾体系，有效预测和指导设计新的用于抑制氮杂环化而剂量式引发高对映选择C-H键氮插入的催化剂提供思路。

Efficient asymmetric insertion into C-H bonds mediated by metal-nitrene has been the critical and hot issue in organic chemistry which fit for the needs of high-efficiency, high-selectivity, atom-economical and environment-friendly. However, there still exist some critical challenges about the mechanism of metal nitrenoid formation and high-selectivity (chemo-, regio-, enantio- and stereoselectivity) have not been resolved. In this project, on the basis of theoretical chemistry, detailed and systematic DFT, Ab initio and QM/QM (MM) studies are presented to understand the mechanisms of metal-nitrene catalyzed C-H amination reactions. All analysis and discussions are on the basis of the four most probable factors involving in determining the mechanism and selectivity: (a) the metal center; (b) the ligand effect; (c) the substituent on the nitrene-N atom; (d) the substituent on the inserted C-H bond. We try to investigate the active species, the reaction reactivity, the multistate potential-energy surfaces, the manner of C-H bond approach to nitrene-N atom, the chemo-, regio-, stereo- and enantioselectivity, and the relationship between the mechanism and selectivity. These fundamental guidelines would help advance the development of efficient and structurally favorable metal-nitrene catalysts for asymmetric insertion into C-H bonds rather than aziridination.