基于优势催化剂发展高效不对称催化反应研究

手性是自然界的本质属性之一。不同构型的手性化合物其对映异构体以不同的方式与受体部位作用可导致不同的效果，不同构型的手性材料具有独特的理化性能。因此，手性物质的合成研究与生命科学、人类健康以及材料科学有着密切的联系。如何合成单一对映异构体的手性分子是化学研究领域的活跃点之一。申请者已发展出一类具有特色和创新性的手性氮氧化合物，它既可作为有机催化剂，也可作为手性配体与多种金属形成配合物催化剂，已在三十多类反应中获得优异的结果，并实现了六类新反应。基于已有的基础，申请者拟继续优化催化剂结构，研究不同中心金属的活化能力，探索新反应，提升已有反应的效率，扩展催化剂的应用范围；同时在实验结果的基础上，通过NMR、X-ray、HRMS和理论计算等来指导修饰和设计新的催化剂，发展高效的不对称催化反应。将发展的方法学应用于重要目标分子的合成，为一些手性药物和重要中间体的合成提供高效的合成方法。

Chirality is a universal phenomenon in nature. Different enantiomers of a given biomolecular can exhibit dramatically different biological activities, and chiral materials with different configurations have uniquely physical and chemical properties. Therefore, chemists are in the endeavor to catalyze reactions with exquisite selectivity for the formation of one enantiomeric form over the other. The applicant has developed a kind of new privileged chiral N,N’-dioxide amide ligands and catalysts. They are enantioselective over more than thirty types of reactions as either chiral ligands or organocatalysts. Six types of catalytic asymmetric new reactions have been realized for the first time. These results encourage the applicant and co-workers to further optimize the structure of chiral N,N'-dioxides, and explore their capabilities in asymmetric reactions with various metal centers. The project will focus on the application extension of the developed catalysts by improving the efficiency and stereoselectivity of some challenging catalytic reactions, as well as the development of new reactions. On the other side, the mechanism of the involved reactions will be investigated by the way of NMR, HRMS, X-ray, and computer calculation, which will help to direct the optimization and design of new catalysts, as well as the development of highly efficient catalytic asymmetric reactions. The developed asymmetric reactions will be used for the efficient construction of optically active intermediates of some important chiral drug molecules and natural products.