手性笼状微反应器的构建及其催化CO2/环氧化物性能研究

Much attention has been paid in the design and synthesis of chiral cage-like micro-reactors due to its great scientific and economic benefits which arising from their application in asymmetric synthesis. Controlled construction of Multifunctional micro-reactors can be obtianed by using chiral and catalytic building blocks. In this project, chiral linear salen-type ligands that containing N-donors can be used as bidentate scaffold for the synthesis of Jacobsen catalysts which are important catalyst in the synthesis of chiral cyclic carbonates by the asymmetric cycloaddition reaction of epoxides with CO2, palladium complexes and tripodal planar pyridine-containing ligands can be used as building blocks in the controlled synthesis of cage-like micro-reactors, molecular templates will be used to avoid the appearing of interpenetration in the controlled assemble of target complexes. In addition, the application of these complexes in the asymmetric synthesis of chiral cyclic carbonate will be studied. In order to get high catalyst stability, selectivity and reactivity, fabrication of the structure and variation of substitute groups on the backbone of the molecular vessels will be also discussed in detail, the catalytic kinetic study will be carried out and the relationship between the structure and catalytic properties will be concluded. The final goal of this project is to develop a method for the controlled construction of chiral cage-like micro-reactors (also high performance catalysts) which can be used as new process for the catalytic synthesis of chiral cyclic carbonate from carbon dioxide and racemic epoxides.

作为一种兼具催化功能的微反应器，手性笼状化合物的构建及其在不对称催化方面的研究具有重要的科学意义和广泛的应用前景。项目针对反应器的功能引入和可控组装问题，拟以Jacobsen催化剂官能团为构建单元实现反应器的催化功能，以手性Salen配体为构建单元实现反应器的多手性中心协同诱导功能，以具有导向配位功能的金属钯为结点、含吡啶官能团线性双齿Salen配体为支撑、平面三齿配体为盖和底，采用模板合成法实现笼状构型多功能微反应器的可控构建；揭示反应器构型与CO2和消旋环氧化物不对称环加成反应的产物选择性和产率之间的构效关系，建立相应的动力学模型，形成基于高选择性、高效微反应器的构造方法。通过本项目的开展，实现兼具催化与手性功能微反应器的可控构建和性能调控，通过动力学模型的建立阐明反应器构型与催化性能的构效关系规律，以期为手性环碳酸脂的制备提供新的制备途径。

作为一种兼具催化功能的微反应器，笼状化合物的构建及其催化方面的研究具有重要的科学意义和广泛的应用前景。项目针对反应器的功能引入和可控组装问题，以金属-Salen催化剂官能团为构建单元实现反应器的催化功能，通过合成一系列的含Salen官能团的“三齿醛”/“三齿胺”、“二齿醛”/“二齿胺”构筑单元，通过胺醛席夫碱反应形成共价键的方式实现3种笼状构型多功能微反应器的可控构建；研究了该系列反应器的气体吸附性能，在该基础上研究反应器构型与CO2和环氧化物环加成反应的产物选择性和产率之间的构效关系，形成了基于高选择性、高效微反应器的构造方法。通过本项目的开展，实现兼具催化功能的微反应器的可控构建和性能调控，为一种气体吸附材料的制备提供思路，为环碳酸脂的制备提供新的制备途径。