【作者】 刘洁；

【导师】 李铁生；

【作者基本信息】 郑州大学 ， 有机化学， 2014， 硕士

【摘要】 本论文合成两种新的具有面手性的催化剂4a1和4a2，利用表面氢引发反应和原子转移自由基聚合反应分别制备了4a2的单分子自组装膜和聚合物刷，并对其制备过程进行了表征。研究了4a2在均相条件下催化偶联反应及聚合物刷和自组装膜的异相催化性质。初步探讨了其在手性催化方面的活性。1.合成了两种不同平面手性的二茂铁环钯化合物（图1），并通过核磁、红外光谱、质谱对化合物结构进行表征，并得到化合物3a2的单晶。在均相体系中，研究了催化剂4a2在水相中催化Suzuki以及Heck偶联反应的催化性能。结果表明催化剂4a2具有很高的催化活性。2.利用表面氢引发反应，制备了催化剂4a2的单分子薄膜，如图2所示。并对各个步骤进行了表征。3.利用原子转移自由基反应将手型单体催化剂直接聚合到固体表面，制备了催化剂4a2的聚合物分子刷，如图3所示。并对制备过程进行了表征。研究了此聚合物刷在水相中催化Suzuki以及Heck偶联反应的异相催化性能。结果表明此聚合刷的催化活性很高，经过条件优化后，产率可达到99%以上。在最优条件下，对此聚合物刷进行了循环催化实验。对于Suzuki偶联反应，可以重复使用8次，产率仍可达到90%以上；对于Heck偶联反应，可以重复使用6次，产率仍可达到90%以上。4．对催化剂4a2以及制备的两种自组装膜的手性催化性能做了初步的探讨。结合文献查阅中的催化剂结构以及催化机理，对手性催化的结果进行讨论。并试图通过对催化剂微环境的改变或是对反应类型的重新选择，以达到选择性手性催化目的。更多还原

【Abstract】 In this paper, two catalysts4a1and4a2having different planar chirality were synthesized and characterized. Two kinds of self-assembly films on hydrophobic and hydrophilic substrate were prepared by hydrogen initiation and atom transfer radical polymerization respectively. Process of fabrication were characterized by AFM, Water contact angle, UV spectrophotometry and cyclic voltammetry method. The chiral catalytic properties of4a2in homogeneous and their self-assembled films in heterogeneous were also investigated.1. Two kinds of planar chiral cyclopalladated ferrocenylimines were synthesized shown in Scheme1and were characterized by NMR, IR, Mass spectrometry. Single crystal of compound3a2was also obtained. In a homogeneous system, the catalyst4a2was used for catalyzing the Suzuki and Heck coupling reaction in water. The results showed that the catalyst4a2has a very high catalytic property, but poor selectivity. 2. Self-assembly film on hydrophobic substrate was prepared by H-surface initiation (Scheme2) and was characterized by AFM, Water contact angle method.3. Catalyst4a2polymer brush was prepared by atom transfer radical polymerization (Scheme3). Process of preparation were characterized. On the other hand, the polymer brush was used for catalyzing the Suzuki and Heck coupling reaction in heterogeneous. Results showed that the polymer brush exhibited high catalytic property and good recycling. 4. The chiral catalytic properties of the catalyst4a2and self-assembled films of4a2were studied preliminarily. Based on literature research and the structure of catalysts and the catalytic mechanisms of chirality catalysis reported in the literatures, the chiral catalytic results were analyzed for trying to change the microenvironment of the chiral catalytic and choose the suitable reaction type to achieve our purpose.更多还原