磁性氧化铁纳米粒子负载手性单膦催化剂的制备和不对称氢化性能研究

项目名称： 磁性氧化铁纳米粒子负载手性单膦催化剂的制备和不对称氢化性能研究

项目编号： No.21202038

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 有机化学

项目作者： 李永

作者单位： 河南教育学院

项目金额： 25万元

中文摘要： 手性催化剂的选择性和催化效率、以及催化剂的分离与回收是目前不对称催化研究领域中最为关键的科学问题。磁性纳米粒子作为催化剂载体，不但具有催化剂负载量大、易分散到溶剂中进行"准均相反应"、稳定性高等特点，更可以利用磁分离技术实现催化剂的分离与循环使用。本课题针对当前均相催化和负载手性催化剂存在的不足，设计合成一类磁性氧化铁纳米粒子负载的手性单膦催化剂。负载的手性配体为具有C2对称连萘或螺环骨架的单齿亚膦酰胺和亚磷酸酯配体。在负载方式上，采用两种方法：一种为通过"Click"反应进行模式化的共价键负载；另一种负载方法为利用氢键或分子识别作用进行非共价键负载。得到负载的磁性纳米催化剂后，将通过NMR、MS、IR、TEM等手段进行结构测试与表征，之后用于官能化烯烃的不对称氢化反应，详细研究它们的催化性能和分离回收情况,以期能综合均相催化和非均相催化的优点，建立一类高效、可回收的手性磁性纳米催化剂新体

中文关键词： 磁性纳米粒子；超分子催化剂；不对称氢化；负载；

英文摘要： Enantioselectivity, efficiency and recycling of chiral catalysts are the most important scientific issues in asymmetric catalytic field. Magnetic nanoparticles have been extensively employed as alternative catalyst supports, in view of their high surface area resulting in high catalyst loading capacity, high dispersion, outstanding stability, and convenient catalyst recycling. To overcome the disadvantage of homogeneous and heterogeneous catalysis, this project mainly designs one kind of magnetic nanoparticle-supported chiral monodentate catalysts and studies their application in asymmetric hydrogenation. The supported chiral ligands are the monodentate phosphoramidite and phosphate with C2 symmetric skeleton. These monodentate ligands are supported to the surface of the magnetic iron oxide nanoparticles by two means: covalent linkage through click reaction and/or self-assembly with complementary noncovalent interactions. Once we get the MNPs-supported catalysts, their structures will be characterized with NMR,IR,MS and TEM. Then the catalytic properties and recycling of these magnetic iron oxide nanoparticle-supported catalysts will be tested in asymmetric hydrogenation of fuctionalized olefin. We expect to develop one kind of magnetic nanocatalyst system with highly catalytic performance and easy recycling, wh

英文关键词： Magnetic nanoparticle；supramolecular catalyst；asymmetric hydrogenation；immobilization；