手性超分子组装体系的动态共价合成及其应用

Asymmetrical catalysis based on chiral catalysts has been widely used in the syntheses of relatively small chiral molecules. However, this approach is not feasible for the preparation of those relatively complex and three-dimensional chiral molecules, on account of the step-wise, tedious nature. In this proposal, the applicant attempts to take advantage of the reversible nature of dynamic bonds, in order to realize the self-assembly of chiral molecules which have complex molecular architectures. In addition, the applicant also attempts to realize the self-assembly of chiral molecules in water, a so-called green solvent, by using a water compatible organic reaction, namely hydrazone condensation. The possibility of using these self-assembled molecules to host a variety of chiral or prechiral guest molecules will also be investigated in both organic solvent and water. Based on the host-guest recognition behaviors, the following functions might be accomplished, including i) separation of enantiomers, ii) asymmetrical catalysis, iii) detection of biological chiral targets.

基于手性催化剂的不对称催化已经被广泛运用于手性小分子的合成。然而，这种方法对于合成复杂三维的手性分子和分子组装体系存在步数多，耗时长等缺点和局限。本项目试图利用动态共价键的可逆性质，实现复杂三维手性分子组装体系的高效合成。并利用酰腙化学键在水中的稳定性，进一步探索手性组装分子体系在水溶液中自组装的可能性，并致力于在水溶液中实现它们对客体分子的识别。利用这些手性组装体对其他手性或者前手性小分子的选择性包结和识别，实现如下功能，包括i）手性小分子的拆分；ii）不对称催化；iii）生物手性分子的检测。

本项目围绕手性分子的动态共价自组装，做出了较为原创性的研究成果。利用亚胺缩合反应的可逆性，高效甚至定量的合成了一系列具有复杂三维结构的手性分子的合成。并利用多重共价带来的稳定性增强效应，实现了在水溶液中完成亚胺缩合反应。并利用疏水作用，实现了自组装分子的客体识别能力和水溶液中拓扑结构复杂分子的自组装。具体的工作包括，1）杯状手性分子的自组装和手性客体分子的拆分；2）四面体分子笼的手性选择性自组装；3）自由基分子的自组装以及手性自分类；4）利用基于酰腙缩合反应的分子笼所进行的客体识别以及ee值测定；5）三叶结分子的自组装和手性精准控制。共发表论文五篇，包括四篇Angew.Chem.，一篇Chem.Eur.J.。