基于非共价相互作用的绿色催化研究

It is of great help to reduce the environmental impact by replacement of hazardous solvents with green ones. Although there are many green solvents, some environmentally hazardous solvents, such as DMF, and nitromethane are still widely used in organic synthesis due to their auxiliary roles in catalysis. Until now, there are very few reports which harness non-covalent interactions to exert control over solvent selection. Moreover, those reports are all related to Brønsted acid catalytic processes. This project attempts to construct solvent moieties into porous polymers, which in turn serve as platforms for introducing catalytic metal species. Due to the high density of the solvent moieties, these porous polymers retain solvation ability, which greatly influences the performance of incorporated active sites via non-covalent interactions. With the aid of this "solvent"-catalyst interactions, some hazardous solvents can be successfully replaced by already existed green solvents in many metal-catalyzed processes. It can be speculated that the upcoming discoveries will extend the application scope of green solvents in synthetic chemistry and provide some useful information to design bifunctional catalysts.

以绿色溶剂代替环境不友好溶剂可以显著减少化学反应对环境的负面影响。受溶剂辅助催化能化差异的限制，尽管有许多绿色介质的存在，DMF、CH3NO2等环境不友好溶剂依然广泛应用于催化合成。目前，利用非共价作用改变反应溶剂选择性的报道很少且局限于Brønsted酸催化。本项目通过设计溶剂官能化高分子负载型金属催化剂，利用催化剂中溶剂片段对催化活性中心的非共价作用辅助催化过程，从而实现用已知的绿色溶剂代替酰胺类溶剂和硝基甲烷分别应用于过渡金属和金属磺酸盐作为Lewis酸催化的反应。本项目研究成果将进一步拓展绿色溶剂在化学合成中的应用范围，同时为多功能催化剂的设计提供一些新的思路。

在催化剂中引入偶极性基团有利于避免有害极性非质子溶剂在有机反应中的使用。本项目分别通过超交联和电子辐照的方法制备出带有酰胺和砜基基团的偶极性催化剂，采用FT-IR光谱、荧光光谱、固体13C NMR以及XPS等表征手段论证极性基团的引入、以及其对催化材料极性的增强效果，通过对照实验揭示了辅助催化及其促进有害极性非质子溶剂替代的作用。接着，我们发展了一系列在绿色介质中合成杂环化合物的新方法。在本项目的资助下，在Green Chem., Chem Commun., ChemSusChem等期刊上发表SCI论文8篇，申请中国专利2件。