具有N-芳基骨架轴手性配体的设计合成及其不对称催化应用研究

This project will focus on the development of novel axially chiral ligands with a N-aryl framework instead of traditional biaryl framework. A series of axially chiral ligands with a N-aryl framework bearing various coordination groups such as N-heterocyclic carbene, phosphine and oxazoline as well as several types of N-aryl axis-unfixed ligands will be prepared in this project. This project will also investigate the atropisomeric behavior of these N-aryl axially chiral ligands, the coordination behavior of these ligands with transition metals, and the application of these ligands in asymmetric catalysis. This project will greatly promote the design of novel axially chiral ligands and their application in asymmetric catalysis, and provide original technology having intellectual property rights for the development of novel and effective axially chiral catalysts.

本项目以新型轴手性配体的开发为研究对象，提出了一类基于N-芳基骨架轴手性配体的设计思路，该类配体的开发将拓宽轴手性配体以联芳基为骨架的设计理念。合成具有N-芳基骨架的轴手性配体，研究它们的消旋行为以及和过渡金属的配位行为，制备N-芳基轴手性金属催化剂并研究其不对称催化应用。本项目的实施将为新型轴手性配体的设计及过渡金属催化的不对称反应研究起到积极作用，为发展新型高效手性配体及过渡金属催化剂提供具有知识产权的源泉技术。

轴手性配体的发展在基于过渡金属催化的不对称应用中占有举足轻重的作用。相比于传统的基于联芳基骨架的轴手性配体，本项目提出了一类基于N-芳基骨架的轴手性配体设计思路。通过有机合成手段，合成了基于N-芳基骨架的轴手性安定配体和轴不安定手性配体。通过和不同的过渡金属如金、钯、铂等配位，在手性恶唑啉配位基团的手性诱导下，获得了一系列具有N-芳基骨架的轴手性配位金属化合物。项目后期进一步研究了上述金属催化剂得不对称应用，如钯催化芳基硼酸的不对称转化和铑催化芳基硼酸的不对称转化等。在本项目基金的支持下，发表了和课题相关的SCI论文7篇。本项目的实施将为新型轴手性配体的设计及过渡金属催化的不对称反应研究起到积极作用，为发展新型高效手性配体及过渡金属催化剂提供具有知识产权的源泉技术。