新型手性配体的合成以及应用

本论文的研究内容主要分为两部分：第一部分详细讨论了新型轴手性配体的合成研究工作；第二部分是新型二茂铁配体的合成以及其在简单脂肪酮中的应用。 第一部分工作是新型轴手性配体的合成。以BINAP为主要代表的轴手性结构配体是一类具有广泛应用的成功配体。BINAP类型配体骨架结构不易变形，具有刚性，芳环骨架具有可修饰性，所以我们设计了一种新型的轴手性配体，从最简单的2，6-二氟苯甲酰氯为起始原料，想通过7步反应制得最终所需要配体，但是遗憾未能在最后一步成功制得。 第二部分是新型二茂铁骨架配体的合成及其在简单脂肪酮中的应用。二茂铁的优点包括：第一，原料价格便宜；第二，结构稳定；第三，富电子。二茂铁的1，2或1，3位置可以被取代基取代，当这些位置被不同取代基取代后，二茂铁会失去其对称面，形成面手性的二茂铁衍生物。手性二茂铁骨架稳定性强，易于合成，是一个具有优势结构的骨架。我们通过对课题组前期工作中所合成的二茂铁骨架配体进行修饰，以及在前期基础上引入新的片段来合成新的二茂铁骨架配体，并将其应用在简单脂肪酮的氢化中。在一个温和的条件下(5 atm，rt)，最后结果显示所制得配体结果最好的对映选择性79%。

The research is mainly divided into two parts: the first part discusses the synthesis of novel axial chiral ligands. The second part is the synthesis of new ferrocene ligands and their applications in simple fatty ketones. The first part of the work is the synthesis of novel axial chiral ligands. Axial chiral ligands represented mainly by BINAP are a kind of successful ligands with a wide range of applications. The skeleton structure of BINAP type ligands is not easy to deform and has rigidity, and the aromatic ring skeleton is modifiable. Therefore, we designed a new type of axial chiral ligand, starting from the simplest 2,6-difluorobenzoyl chloride as the starting material, I wanted to synthesize the final ligand through a 7-step reaction, but unfortunately it was not successful in the last step. The second part is the synthesis of a new type of ferrocene skeleton ligand and its application in simple fatty ketones. The advantages of ferrocene include: First, the raw material is cheap. Second, the structure is stable. Third, it is rich in electrons. The 1, 2 or 1, 3 positions of ferrocene can be substituted by substituents. When these positions are substituted by different substituents, the ferrocene will lose its symmetry plane and form a chiral ferrocene derivative. The framework of chiral ferrocene has strong stability and is easy to manufacture. It is a framework with advantageous structure. We modified the ferrocene framework ligand synthesized in the previous work of the research, and introduced new fragments on the basis of the previous stage to synthesize new ferrocene framework ligands, and applied them to the hydrogenation of simple fatty ketones. among. Finally，Under a mild condition (5 atm, rt), the result shows that the obtained ligand has the best enantioselectivity of 79%.