基于手性二茂铁骨架的多功能有机膦催化剂构建及其在不对称MBH反应中的应用研究

项目名称： 基于手性二茂铁骨架的多功能有机膦催化剂构建及其在不对称MBH反应中的应用研究

项目编号： No.21472240

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 姜茹

作者单位： 中国人民解放军第四军医大学

项目金额： 40万元

中文摘要： 不对称有机催化是当今有机化学最为活跃的研究领域之一，已与金属催化和酶催化一起成为不对称催化的三大支柱。然而，迄今报道的手性有机催化剂大多衍生于有限的几种手性骨架，而在手性金属催化剂设计中被视为"优势骨架"的二茂铁，作为有机催化剂的骨架却鲜有报道。课题组前期研究发现：双功能二茂铁有机催化剂能高对映选择性地催化一些不对称反应进行，预示二茂铁极有可能是构建有机催化剂的一个理想骨架。在此基础上，本课题模拟生物酶多功能活化的特点，在二茂铁骨架上首次引入多种立体基因及多种功能基（LB、BA、BB功能基），构建一系列结构新颖的多功能二茂铁类有机膦催化剂，并将其用于多种底物的不对称MBH反应中，系统考察多个立体基因的相互匹配以及多种功能基的协同作用，以期筛选出催化活性高、立体选择性好的二茂铁类有机催化剂。本研究将为二茂铁类有机催化剂的开发进行有益的探索，为手性有机催化剂设计提供更多的优势骨架及结构模式。

中文关键词： 不对称有机催化；二茂铁；手性膦催化剂；多功能；不对称MBH反应

英文摘要： Asymmetric organocatalysis has become one of the most fascinating area in organic chemistry research and grown into three pillars of asymmetric catalysis together with biocatalysis and metal catalysis. So far, numerous organocatalysts have been rooted in several core structures. Surprisingly, ferrocene, a "privileged framework" for the construction of effective chiral ligands in metal catalysis, has not been exploited as a backbone of organocatalysts. Our previous study showed that bifunctional ferrocene organocatalysts would be a potential "ideal framework and model" for the construction of organocatalysts. In this project, a series of novel ferrocene-based multifunctional chiral phosphine organocatalysts, possessing with various stereogene and multiple functional groups (such as Lewis base, Bronsted acid, and Bronsted base), were designed and synthesized in accordance with simulating the characteristics of enzyme mutifunctional activation. Their performance (enantioselectivities and catalytic activities) in asymmetric MBH reaction would be evaluated. It would be systematically investigated for the first time that the matching of the various stereogene and the cooperation of the multi- functional groups of a series of ferrocene-based organocatalysts on enantioselectivities and catalytic activities. This study w

英文关键词： asymmetric organocatalysis；ferrocene；chiral phosphine catalyst；multifunctional；asymmetric MBH reaction