可控微观结构高分子手性催化剂的合成及催化性能的研究

A major problem associated with most homogeneous catalyst systems is the separation and recycling of the expensive chiral catalyst. A common solution to this problem is to "heterogenize" a homogeneous catalyst by anchoring the catalyst on an organic or inorganic insoluble support. Unfortunately, despite the advantage of easy separation, the use of insoluble supported catalysts suffered from lowered catalytic activity and stereoselectivity. The leaching of the noble metal catalyst from the support was also a significant problem. In this study, we used soluble polymer as an alternate support. Seven kinds of soluble polymer or dendrimer-supported ligands and their metallic catalysts have been prepared. These novel catalysts were found to be highly effective and recyclable. Some of them even showed higher activity and/or enantioselectivity as compared with the corresponding homogeneous catalyst. Among these catalysts, the Ru(BINAP)-centered dendritic catalysts were synthesized for the first time. It was found that their catalytic activity increased with the increase generation. This finding showed that the dendrimer catalyst has the potential to combine the advantages of homogeneous and heterogeneous catalysis. Therefore, it have been demonstrated that the soluble polymer-supported chiral catalyst, in particularly the chiral dendritic catalyst, are of high scientific and industrial values.

以树状结构大分子和螺旋链光学高分子为载体合成微观有序、结构可控的高分子手性膦金属催化剂；研究高分子载体的微观结构与催化性能的关系；通过高分子载体的结构调控和修饰优化催化性能；发展高效的、易于分离的高分子手性膦金属催化剂体系以及新的合成方法。本项目的研究成果对新一代高分子手性催化剂的设计有重要的理论意义，同时又有实际应用价值。