超分子凝胶的构筑、组装调控及其在仿生催化氧化反应中的应用

The functional application of supramolecular gels in chirality is of fundamental interest in the community of supramolecular chemistry, nanotechnology and materials science. Herein we will design and synthesize a series of gelators derived from nature-occuring aminoacid based the concept of two-component gels. We envisioned that these gelators could co-assemble with manganese porphyrins to form two-component supramolecular gels, and supramolecular chirality could be obtained by means of intelligent design and modulating. In addition, high-valent manganese-oxo species will be generated and characterized with all kinds of spectroscopic methods, both spectroscopic characterization and kinetic studies are applied to understand their properties, allowing us to learn how to generate and manage high-valent manganese-oxo intermediates in a controlled manner and use them in the selective oxidation of organic substrates. Employing a bioinspired approach, we will design a asymmetric oxidation system based on supramolecular gels in which water will be used as an oxygen source, thus developing a environmentally benign asymmetric oxidation system and realized the chirality transfer from molecular chirality to supramolecular chirality and to molecular chirality again.

超分子凝胶的手性功能应用具有重要的科学意义。本项目基于双组份凝胶的概念，拟设计合成基于氨基酸的胶凝剂分子，与非手性的锰卟啉分子共组装形成双组份超分子凝胶，通过调控组装过程，构筑手性纳米结构，诱导产生超分子手性，研究手性纳米结构产生的机理，并创新性地将超分子凝胶应用到以水为氧源的仿生不对称催化氧化反应中，从而构建绿色催化选择氧化反应新体系，实现手性信息从超分子水平到单分子水平的传递表达。以反应机理研究为导向，制备并表征基于超分子凝胶的高价锰-氧配合物，综合各种谱学表征和反应动力学研究明确高价锰-氧中间体的生成和反应性规律，阐明超分子凝胶的催化作用机制，揭示凝胶内部手性纳米结构与催化性能之间的构效关系，为基于超分子凝胶的仿生催化体系的设计提供指导。

本项目设计合成了基于天然氨基酸的两亲性胶凝剂分子和磺酸官能化的非手性锰卟啉分子，自组装形成超分子凝胶，通过调控组装过程，构筑手性纳米结构，诱导产生超分子手性，并将其应用于以水为氧源的烯烃不对称环氧化反应，实现了手性信息由分子水平到超分子水平再到分子水平的传递。在此基础上，我们还发展了Zr(IV)-salan催化的β-酮酸酯的高对映选择性氧化α-羟化反应、非血红素铁催化烯烃不对称顺式双羟化反应以及非血红素锰催化脂肪族C(sp3)‒H选择氧化羟化等仿生催化氧化反应新体系。. 在本项目的资助下，目前已在Coord. Chem. Rev., Adv. Synth. Catal.等期刊发表论文4篇，申请中国发明专利1件。