X-H(X=N、C及O)插入反应是构建碳-碳及碳-杂原子键的重要途径。含酰胺的手性胍化合物与金属试剂相结合，可形成性能优异的不对称催化剂，高效、高选择性地实现重氮化合物的不对称X-H插入反应。本项目采用量子化学计算方法，研究含不同分子骨架及取代基的典型手性胍化合物与Cu(I)、Cu(II)及Rh(II)等形成的配合物的空间结构和电子性质，及其在不对称X-H插入反应中催化作用本质和特点，揭示金属配合物结构与活性之间的关系、手性诱导效应产生的原因和传递的关键。探明反应底物(重氮酯、胺、羧酸及端基炔)与配合物的相互作用规律，总结出催化剂对关键中间物种形成、产物选择性控制及调变规律。进一步考察溶剂、抗衡离子、添加剂等对手性胍、反应底物与金属中心配位作用的影响。在此基础上进行新型手性胍及金属配合物的设计及合成，并将其用于不对称X-H插入反应实验研究，为进一步研制高效不对称合成催化剂提供知识积累。

X-H insertion reaction (X=N, C and O) provides an important method to construct C-X bond. The combination of chiral guanidine-amide compound with metal reagent could form efficient catalysts for asymmetric X-H insertion reaction of α-diazoesters, affording products with good yields and excellent stereoselectivity. The key of this work is to investigate the structures and electronic properties of metal catalysts formed by coordinating the typical chiral guanidine with different subunits and substitutes to metal reagents of copper(I), copper(II), as well as rhodium(II). Furthermore, the relationship between geometrical factor and the activity of catalysts is explored, and the key factors for the chirality transfer are understood. The universal rules involving in the interaction between chiral guanidine-metal complex and substrates (diazoester, amine, carboxylic acid, 1-alkyne) as well as essence and features of catalysis in asymmetric N-H insertion reaction are studied. The influence of catalysts on the formation of key reactive species, chemoselectivity and enantioselectivety of products will also be explored. Additionally, effect of solvent and counterion on the interaction between ligand, metal center and substrate will be considered. Based on these results, new chiral guanidine compounds and guanidine-metal catalysts for asymmetric X-H insertion reaction will be designed and synthesized to provide useful hints for developing high efficiency chiral guanidine catalysts for asymmetric synthesis.