手性超分子自支撑薄膜的不对称催化

项目名称： 手性超分子自支撑薄膜的不对称催化

项目编号： No.20803084

项目类型： 青年科学基金项目

立项/批准年度： 2009

项目学科： 轻工业、手工业

项目作者： 张莉

作者单位： 中国科学院化学研究所

项目金额： 21万元

中文摘要： 手性是自然界的重要课题，可在不同层次上，如单分子，超分子，纳米尺度上表现出来。手性从单分子到超分子及到纳米尺度的传递已经有研究报道，但手性从超分子层次传递到单分子层次上，还没有足够的研究，超分子不对称催化就是手性从超分子到单分子层次传递的有效途径。本项目从小分子出发，通过分子间的弱相互作用组装手性超分子结构，首先研究手性超分子结构产生的机理，及手性结构的动态形成机理。并继续将金属和手性两种在不对称催化中至关重要的元素组装在一起，组装成含有金属活性中心的手性超分子，研究其对氨基酸等的手性识别作用，为手性催化的研究奠定了一定基础。再把此手性超分子作为催化剂引入到不对称合成中，制备手性对映体，系统模拟了自然界中手性的从无到有，及自催化作用，对手性起源的问题做以初步探讨。

中文关键词： 手性；自组装；超分子催化

英文摘要： Chirality is an important symmetry property of many daily-life objects and chemical compounds. The chiral asymmetric catalysis is the most important method in the preparation of enantiomerically pure compounds. In this project, we aimed to explore various mechanisms for the transfer of stereochemical information to and from the supramolecular level. Two aspects are discussed: the assembly of chiral supramolecules and chirality at the supramolecular level being transferred to the molecular level through chiral catalysis. We have investigated the self-assembly and induced supramolecular chirality of a dianionic meso-tetraphenylsulfonato porphyrin (TPPS) on the peptide or induced by ionic liquids. In addition, we have shown that the introduction of Cu2+ into a glutamic acid-based bolaamphiphilic lipid caused the formation of the nanotube with multilayer wall. Such nanotube showed enhanced asymmetry catalytic behaviors and accelerated the asymmetric Diels-Alder cycloaddition between cyclopentadiene and aza-chalcone. The nanotubular structures, which provided a high density of catalytic sites and chiral microenvironment suitable for asymmetric reaction, benefit for the enantiomeric selectivity. Six SCI papers were published through the project. The project fulfilled its designed mission.

英文关键词： Chirality; Self-assembly;Supramolecular catalysis