【作者】 刘强；

【导师】 景欢旺；

【作者基本信息】 兰州大学 ， 物理化学， 2011， 硕士

【摘要】 在当今社会,低碳经济受到大家的普遍关注,而二氧化碳作为丰富的碳资源,它可以作为原料合成环碳酸酯这类重要的化合物,环碳酸酯可以作为极性有机溶剂、有机合成的中间体以及聚碳酸酯的单体等,手性环碳酸酯又可以制备手性药物等,在本论文中,我们主要以环氧化合物的动力学拆分为研究主题,主要包括以下四章：第一章：对环碳酸酯的合成方法进行了综述,并对二氧化碳与环氧化合物的动力学拆分得到手性环碳酸酯的研究进行了简要介绍。第二章：设计合成了手性氨基酸修饰的单体双席夫碱钴(SalenCo)催化剂,并将其用于二氧化碳和环氧化合物的动力学拆分中,讨论了在不同手性催化剂、共催化剂、抗衡离子、反应温度对手性环碳酸酯ee值的影响,并且在25℃得到48.6%的产率,60.2%e.e.值的手性环碳酸酯。第三章：设计合成了双醛聚合的氨基酸双席夫碱钴(SalenCo)催化剂,分子量达到17202,应用到二氧化碳与环氧化合物的不对称环加成反应,同时研究了不同手性催化剂、抗衡离子、共催化剂、反应温度对生成光活性环碳酸酯的影响,并且对催化剂进行了循环利用,在重复使用五次以后催化活性和对映选择性没有明显降低。第四章：设计合成了氨基酸修饰的末端烯烃Salen,把它用两种方式进行聚合：一是自身聚合得到均相催化剂,分子量为24218；二是和苯乙烯聚合得到非均相催化剂。将聚合催化剂在不对称催化中进行了应用。更多还原

【Abstract】 In today’s society, low-carbon economy has been the general concerned by everyone, and carbon dioxide as a rich carbon resource, it can be used as raw material in the synthesis of cyclic carbonates, such important compounds, can be used as polar organic solvents, intermediate in organic synthesis and monomer for polycarbonate, and chiral cyclic carbonate also can be prepared in chiral drugs, and so on. In this thesis we mainly study on the kinetic resolution of epoxides, including the following four chapters:Chapter 1:The syntheses of cyclic carbonate are reviewed, in which, the kinetic resolution of epoxides by carbon dioxide is briefly introducted.Chapter 2:The Salen-type ligands and their cobalt Salen catalysts modified by chiral amino acid were designed, synthesized and applied in the kinetic resolution of epoxides by carbon dioxide. Various effects of chiral catalysts, co-catalysts, counterious, reaction temperatures on the asymmetric cycloaddition of racemic epoxides were investigated and discussed. The chiral propylene carbonate was obtained in 48.6% yield and 60.2% ee value at 25℃.Chapter 3:The dialdehyde polymeric of Salen-type ligands and their catalysts modified by chiral amino acid were designed, synthesized which molecular weight reached 17,202, and applied in the asymmetric cycloaddition of epoxides and carbon dioxide. Various effects of chiral catalysts, counterious, co-catalysts, reaction temperatures on the asymmetric cycloaddition of racemic epoxides were investigated and discussed. The catalysts could be readily recovered and reused five times without loss of either activity or enantioselectivity.Chapter 4:The Salen-type ligands modified by the internal olefins of the amino acid were designed and synthesized. It polymerized in two ways:First, heterogeneous catalyst was obtained by self polymerization, and its molecular weight reached 24,218; Second, heterogeneous catalyst was obtained by copolymerization with styrene. Those polymeric catalysts were applied in the asymmetric catalysis.更多还原