烃类化合物高效不对称催化氧化反应研究

烷烃C-H的催化氧化是非常重要的化学反应，但由于烷烃C-H键的反应惰性，温和条件下实现该反应非常困难。因此烷烃C-H键的催化氧化，尤其是不对称氧化仍是一个非常具有挑战性的研究目标。本项目将致力于开展烷烃C-H键的不对称催化氧化反应研究。在本课题组非血红素铁、锰的合成及催化氧化工作基础上，通过设计合成基于不同二胺骨架（手性）四氮配体及其相应Fe 、Mn等金属配合物，探究二胺骨架以及配体上所带取代基（电子效应、位阻效应）对烷烃C-H键的不对称氧化反应的立体选择性控制和催化活性的影响，从分子水平上深入理解手性配体结构与催化性能之间存在的规律性认识，从而构建高效、高对映选择性的烷烃C-H键的直接不对称氧化反应新催化体系。

The catalytic oxidation of C–H bonds of alkanes is an important reaction, however, the catalytic oxidation of C–H bonds is extremely difficult under mild conditions because of the lack of the reactivity of alkanes. Therefore, the catalytic oxidation, and in particular asymmetric oxidation of alkanes remains a challenging target. This project will aim to study the catalytic asymmetric oxidation of C-H bonds of alkanes. Based on our previous research work of the synthesis of the non-heme iron, manganese complexes and catalytic oxidation reactions, a series of tetradentate nitrogen ligands derived from various diamine and heterocycle with different sp2 nitrogen together with their iron manganese metal complexes will be designed and synthesized. These complexes will be subjected to the asymmetric oxidation of C-H bonds of alkanes to explore the effects of diamine skeleton and substituents (electronic effect and steric effect) of the ligands on the stereoselectivity and the catalytic activity. It will help us to get insight into the relationship between the structure of chiral ligands and catalytic performance from the molecular level. Finally, a novel catalytic system aiming at highly efficient and enantioselective oxidation of C-H bonds of alkanes will be developed.