动态可控的轮烷超分子催化体系的设计与合成

Supramolecular catalysis has become a hotspot in the field of supramolecular chemistry and catalytic synthesis. Design and synthesis of the novel and more efficient supramolecular catalysts are the critical points of supramolecular catalysis.This proposal aims to design and synthesize a new-type of dynamically controllable supramolecular catalytic system, which was designed by using dynamic rotaxanes molecules as the skeleton. The supramolecular catalytic system includes multiple catalytic sites, such as ureido (thiourea), guanidine and so on, in which the conformation of rotaxane was controllable by adjusting the pH value or by ion regulation, and thereby selectively release or close the catalytic sites to achieve the controllable catalytic process. The research content includes: (1) Synthesize the axial molecule which contains active catalytic sites, such as ureido (thiourea), guanidine and so on, and also synthesize the macrocyclic molecule which contains phosphine oxide and 2,6-pyridinediamide functional groups in the macrocycle; (2) Study the assembly process between the axle and the macrocycle, and further investigate the main factors that affect the shift of macrocycle along the axle; (3) Investigate the applications of such dynamic rotaxane-based supramolecular catalyst for synthesizing heterocycle, especially those biologically active heterocyclic framework and functional system. This proposal combines the properties of dynamically controllable rotaxanes and organocatalysis into one system, hoping to achieve the dynamically controllable and site-specific catalytic systems.

超分子催化化学近年来已成为超分子化学和催化合成领域的研究热点。新型、高效的超分子催化剂的设计和合成则是超分子催化化学的核心。本项目旨在设计以动态轮烷分子作为骨架、可以动态调控的新型超分子催化体系，体系包含有多个催化位点,如脲基（硫脲基）、胍基等。通过调节体系pH值或者离子调控来控制轮烷的构象，从而选择性地释放或封闭催化位点，以完成反应的可控催化。主要研究内容包括：（1）设计含有脲基（硫脲基）及胍基等具有催化活性位点的轴分子以及含磷氧和吡啶二酰胺的环分子；（2）组装得到目标轮烷分子，并考察影响环状分子在轴分子上移动的主要因素；（3）将此类动态轮烷超分子催化剂应用于杂环，特别是具有生物活性的杂环骨架的合成及功能化体系中。本项目将轮烷动态可控的性质与小分子催化相结合，希望实现催化体系的动态调控和定点催化。

本项目旨在设计新型动态可控的超分子体系并用于超分子催化，取得主要成果如下：（i）利用脂肪族烷基链与柱芳烃空腔之间所存在的主客体作用，以脲基为桥连基团合成自锁型的[1]索烃；以酰胺为桥连基团合成自锁型的[1]轮烷；（ii）将二苄胺、脲基、磷氧基团作为三个识别位点，按照它们与环组分络合能力由强到弱的顺序进行排列，合成了[2]轮烷型三稳态分子梭。通过酸碱调控和离子调控的方法，实现环组分从三稳态轮烷一端的胺基识别位点经停中间的脲基识别位点后，移动到磷氧识别位点，实现分子梭的定向移动；也实现环组分从胺基识别位点出发，不在脲基识别位点停留直接移动到磷氧识别位点；（iii）合成基于32-冠-10冠醚的联萘酚桥联的穴醚主体，并通过加入酸/碱调控穴醚与氮杂环客体之间形成的准[2]轮烷，准[2]轮烷的形成与解离过程具有荧光响应性，这为进一步发展基于穴醚主体可视化动态催化体系提供重要的参考意义。项目执行期间共发表论文12篇，其中作为通讯作者发表论文11篇, 包括：Chem. Commun.(3); Tetrahedron Lett. (1); Macromolecular Rapid Communications (1); Dyes and Pigments (1); New J. Chem. (1); Polymer Chem. (1); ChemPhysChem (1); Chinese Chemical Letter (2).

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