负载型手性催化剂的制备和不对称串联反应的研究

发布时间：2018-07-20 20:08

【摘要】：一锅催化反应由于其具有原子利用率高和操作步骤少的特点已经吸引很多研究者的关注。然而,昂贵的有机金属配合物和产品污染等固有的缺点,阻碍了其在工业过程中应用。因此,发展一个把金属固载化的策略克服这些缺点是非常有必要的。介孔硅材料作为一种支持固定有机金属配合物在催化中显示了一些良好的功能,而其中蛋壳结构的纳米材料,它具有可移动的功能化的核和外层包覆着功能化的壳,赋予了它在纳米材料上的独特特性,使得蛋壳结构纳米材料在催化领域得到了广泛应用。本论文主要分为以下两部分:(1)双功能负载型金属催化剂的制备及其在Sonogashira偶联-不对称氢转移串联反应的应用:我们利用蛋壳结构材料而设计了一种双功能的异相催化剂,克服了钯钌双金属化合物的不兼容性,从而实现了钯催化Sonogashira偶联及钌催化的一锅不对称氢转移反应。因为蛋壳结构的独特性质,双功能催化剂可以将金属钯和钌分别负载于蛋壳材料的壳与核上,从而可以在偶联及其一锅不对称催化构建炔醇起到协调作用,且目标产物ee值可高达99%。此外催化剂可以回收利用,而且至少循环使用八次而催化剂的催化活性没有明显下降。(2)双功能负载型金属催化剂的制备及其在Suzuki-Miyaura偶联-不对称氢转移串联反应的应用:我们通过一种简单的方法成功合成了一种负载纳米钯粒子及手性钌金属的双功能催化剂,并将催化剂应用于Suzuki偶联及其不对称串联反应中,实现了一锅一步合成手性联芳醇,且目标产物ee值可高达97%,此外催化剂循环使用多次后而催化剂的催化活性没有明显下降。
[Abstract]:One-pot catalytic reaction has attracted the attention of many researchers due to its high atomic utilization and low operational steps. However, its application in industrial processes is hampered by the inherent disadvantages of expensive organometallic complexes and product pollution. Therefore, it is necessary to develop a strategy of metal immobilization to overcome these shortcomings. Mesoporous silicon, as a support for the immobilization of organometallic complexes, has shown some good functions in the catalysis. Among them, the eggshell nanomaterials have movable functionalized nuclei and outer layers coated with functionalized shells. Because of its unique properties in nano-materials, eggshell nanomaterials have been widely used in the field of catalysis. This thesis is divided into the following two parts: (1) preparation of bifunctional supported metal catalyst and its application in Sonogashira coupling-asymmetric hydrogen transfer series reaction: we designed a bifunctional heterogeneous catalyst using eggshell structure. The incompatibility of palladium and ruthenium bimetallic compounds was overcome, and palladium catalyzed Sonogashira coupling and ruthenium catalyzed one-pot asymmetric hydrogen transfer reaction were realized. Because of the unique properties of the eggshell structure, the bifunctional catalyst can load palladium and ruthenium onto the shell and nucleus of the eggshell material respectively, which can coordinate the formation of acetylene alcohol in the coupling and its one-pot asymmetric catalysis. The ee value of the target product can be as high as 99%. In addition, the catalyst can be recycled, Moreover, the catalytic activity of the catalyst did not decrease significantly without at least eight cycles of recycling. (2) preparation of the bifunctional supported metal catalyst and its application in Suzuki-Miyaura coupling-asymmetric hydrogen transfer series reaction: we adopted a simple Methods A bifunctional catalyst supported on nanometer palladium particles and chiral ruthenium metal was successfully synthesized. The catalyst was used in Suzuki coupling and its asymmetric series reaction to realize the one-pot one-step synthesis of chiral biaryl alcohol, and the ee value of the target product could be as high as 97%. In addition, the catalytic activity of the catalyst did not decrease obviously after repeated cyclic use of the catalyst.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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