新型有机介孔材料功能化固载Au(I)催化剂制备及性能研究

Along with the vigorous development of the green chemistry, gold catalysts show many valuable features and the exploitations of gold catalysts for commercial applications are being pursued. It is also at the heart of a number of new developments in green technology and the area of gold catalysis is sometimes referred to as a "foundational pillar" of green chemistry. Recently there has been an increasing of interest in the chemistry of gold compounds in general and a significant portion of the new research activity has been contributed by cationic gold(I) complexes. Cationic gold(I) complexes have emerged as powerful homogeneous catalysts for the electrophilic activation of carbon-carbon multiple bonds towards nucleophiles to promote a number of unprecedented chemical transformations. Immobilization of the gold(I) complexes onto solid supports would facilitate the recovery and reuse of these precious catalysts in practical synthesis. Many research efforts on the heterogeneous gold-catalyzed reactions have been dedicated to the gold particles and the study of the immobilization of the gold(I) complexes have only just a few studies as yet. Our research emphasizes on the immobilization of the gold(I) complexes based on the correlative researches which have been reported. We choose the mesopolymers as a new solid support. The organic framework of the mesopolymers can provide numerous opportunities to tailor the chemical properties through the incorporation of a wide variety of useful organic functional groups by grafting or co-condensation. We aim at developing new, highly effective and remarkably heterogeneous Au (I) catalyst systems which will be recoverable and the reaction mechanism is also needed to be investigated. On this basis we will develop a series of heterogeneous Au (I) catalyst systems which is suitability by changing the supports or the ligands in the catalyst.

金催化剂的基础及应用研究是当前绿色催化研究的热点之一。可溶性金络合物催化剂的用途非常广泛，其中Au(I)催化剂及相关反应的应用研究正备受关注，实现Au(I)催化剂的固载化，是极富挑战性的难点和热点。本课题研究拟在现有此类研究的基础上，侧重利用有机介孔材料骨架表面丰富的官能团和足以提供准均相环境的介孔孔道，实现Au(I)催化剂的化学功能化固载和介孔反应空间的统一，构筑Au(I)功能化的新型多相催化体系。通过比较及多模板反应的考察揭示影响催化剂反应性能(包括稳定性)的关键因素，研究新型催化材料的反应机理，考察循环使用性能，并在此基础上通过筛选新载体及设计合成新的配体制备系列Au(I)催化剂，研制具有普适性的催化反应体系。

金催化剂由于其优异的催化性能和特殊的反应选择性，近年来已经成为金属有机化学领域的研究热点。将金催化剂多相化可以解决其不能重复使用的问题。项目以此为目标，发展了一系列固载型金催化剂的合成方法，并拓展了合成高附加值精细化学品的新途径。研究内容主要包括：（1）固载型金催化剂的合成和表征及催化性能和循环性能考察。合成一系列FDU有机介孔材料固载Au(I)催化剂，并扩展催化剂应用范围，在烯丙醇胺化反应、δ-羟基共轭炔酮类化合物分子内环化等反应中研究其催化及循环性能，首次合成了11种α-芳基-γ-吡喃酮类化合物。催化剂可以循环使用。在共轭烯炔酮类化合物亲电加成反应中，我们还发现SBA-15固载的金催化剂，其载体对烯炔酮与甲醇的反应具有一定的促进作用。（2）固载型手性金催化剂催化的不对称催化反应。制备了含有手性亚磺酰胺类膦配体的高分子聚合物固载的Au催化剂。该催化剂能够高收率高选择性实现烯炔酮与硝酮的[3+3]不对称环加成，并可实现八次循环。同时还制备了SBA-15固载的手性金催化剂，在不对称环加成反应中也有较好的对映选择性。（3）新型金属-配体体系催化的高原子经济性的绿色催化体系合成多种高附加值精细化学品。为了筛选合适金属-配体体系进行固载，我们发展了多个新型的高原子经济性的绿色催化体系，用于合成多种高附加值精细化学品。（4）咪唑功能化有序介孔酚醛树脂材料的制备、表征及应用。制备了一系列咪唑类离子液体功能化的有序介孔材料，在CO2环加成反应中表现出的良好的催化性能。催化剂可循环使用，活性没有明显降低。FDU载体的介孔有机骨架以及丰富的酚羟基极大地促进反应的进行。在此基础上，通过溶剂挥发诱导自组装的方法，一步制备了一系列咪唑功能化有序介孔材料。对材料进行简单修饰后在催化二氧化碳环加成反应中显示出极高的催化活性。项目取得的成果在均相催化剂工业化利用方面具有一定的理论和现实意义。