有机催化可见光敏化分子氧的不对称氧化反应研究

项目名称： 有机催化可见光敏化分子氧的不对称氧化反应研究

项目编号： No.21476041

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 有机化学

项目作者： 孟庆伟

作者单位： 大连理工大学

项目金额： 84万元

中文摘要： 有机催化的不对称氧化反应是直接构建手性羟基化合物的重要反应之一，在不对称有机催化领域有着重要位置。目前只有少数氧化剂可用于该反应，受到氧化剂类型的限制，有机不对称氧化反应还存在反应难以控制、反应时间长、温度低等问题，因此急需开发新型氧化体系，实现条件温和、低能耗、原子经济性的绿色有机不对称氧化过程。 可见光光敏氧化是以易得、绿色、廉价可见光为源，激活分子氧作为氧化剂进行氧化。本项目创新性的将可见光光敏氧化方法应用到有机催化的不对称氧化体系中，以β-酮酸酯类化合物的不对称α-羟基化为模型反应，探索催化剂结构、光敏剂结构、底物结构以及溶剂效应对反应活性和对映选择性的关系，明确分子氧的活化形式与转化途径，扩展底物适用类型，揭示光敏化氧化体系与有机不对称催化体系之间的相互作用规律，实现两个反应体系的协同作用，为应用分子氧和可见光的绿色原子经济性的不对称光敏化氧化反应奠定理论基础。

中文关键词： 有机催化；可见光；羟基化；不对称合成；光敏化氧化

英文摘要： As one of the most important process to produce chiral hydroxy, organcatalytic enantioselective oxidization play a vital role in the fields of asymmetric organocatalysis. Because of the limit of oxidants, there are some deficiencies in asymmetric oxidization. For example, some oxidation reaction need lower reaction temperature, longer reaction period and difficult to control. Thus, new type of asymmetric oxidation methodologies characterized by low environmental impact, reduced costs of energy, high atom-economy need to be established by using novel oxidants. In this project, photosensitized oxidation, an advanced oxidation processes using molecular oxygen as oxidant and visible light as energy, was applied to the field of organcatalytic enantioselective oxidization. In order to reveal the law of the interrelationship between organocatalysts, photosensitizers, substrates, solvents, reaction activity and enantioselectivity, organocatalytic enantioselective photooxygenation of β-keto esters was used as the model reaction. Then investigating the transformation means of molecular oxygen and expanding the substrates scope. This project aims to ensure photosensitized oxidation and organcatalytic enantioselective oxidization can work together efficiently, and further to establish the theoretical foundation for the development of low environmental impact, reduced costs of energy, high atom-economy organcatalytic enantioselective photosensitized oxidation with high efficiency, high activity and high enantioselectivity.

英文关键词： organocatalysis;visible light;hydroxylation;asymmetrical synthesis;photosensitized oxidation