【作者】 刘莎莎；

【导师】 刘波；

【作者基本信息】 哈尔滨理工大学 ， 材料物理与化学， 2006， 硕士

【摘要】 1,3-偶极环加成反应是有机化学基础理论及合成方法研究中起重要作用的一个反应。硝酮与烯烃的反应是环加成反应中研究最多的一种反应。硝酮作为1,3-偶极试剂与不饱和烃加成生成异恶唑类杂环化合物。在合成结构复杂的天然产物等方面具有很大的应用价值。近几年来,1,3-偶极环加成反应的对映选择性金属配合物催化得到了较多研究。人们研制出了一系列控制反应立体选择性的金属配合物催化剂,尤其是对硝酮和链烯烃反应,许多催化剂对Diels-Alder反应和1,3-偶极环加成反应同时具有较高的对映及非对映选择性。本文中的理论计算是在SGI公司的orange3800型服务器上进行的,软件使用Materials Stodio程序包。采用理论计算的方法研究了Cu(II),Zn(II)-手性二噁唑啉络合物与N-苄基-α-乙氧酰基硝酮形成的反应前驱体与乙基乙烯基醚的1,3-偶极环加成反应过程。讨论了反应前驱体的前线轨道和优化的分子结构对环加成反应的速度和立体选择性的影响,对手性金属催化剂存在下的1,3-偶极环加成反应的立体选择性进行合理解释。本文还讨论了催化反应和非催化反应速率对反应立体选择性的影响。更多还原

【Abstract】 1,3-dipolar cycloaddition reaction is the most useful reaction in fundmental theory of organic chemistry and organic synthesis. The 1,3-dipolar cycloaddition of nitrones with alkenes is one of the most studied reactions, among all the cycloadditions. It provides the most efficient method to prepare isoxazolidines that are widely used as starting compounds in organic synthesis, in particular for building natural products.The rapid developments of complex in the field of catalytic enantioselective 1,3-dipolar cycloaddition reactions which have occurred during the recent years are reported.A series of catalysis has been applied for 1,3-dipolar cycloaddition reactions of nitrons with electron-deficient and electron-rich alkenes, respectively. In several cases a high degree of control of both thediastereoiosmer and enantioselectivity has been achieved in both Diels-Alder reactions and 1,3-dipolar cycloaddition reactions.In this thesis, theoretical study approach has been used to study with Materials Stodio on the workstation sgi3800.Theoretical investigations are carried out on the cycloaddition reaction between vinyl ethyl ether and the pro-formed complexes which formed by the reaction of chiral copper(II)- or zinc(II)-bisoxazolines with N-benzyl-C-ethoxylcarbonyl nitrone. The influences of the frontier molecular orbitals and optimizing geometry of the pro-formed complexes on the reaction rates and endo/exo selectivity are discussed, and a reasonable explanation about the steroselectivity of 1,3-dipolar cycloaddition reaction in the presence of copper (II)- or zinc(II)-bisoxazolines catalyst is given. The influence of catalytic and no-catalytic reaction rate on the steroselectivity is also discussed.更多还原