【作者】 刘波；

【导师】 张明杰；

【作者基本信息】 天津大学 ， 有机化学， 2008， 博士

【摘要】 本论文设计并合成了5种Schiff碱及其稀土配合物,研究了配合物在催化环氧氯丙烷的立体选择性水解动力学拆分和不对称Biginelli反应中的应用。一、配体及其配合物的合成与表征以自制的胺为主体,合成并表征了5种手性Schiff碱配体:L1:(+)-(R)-1, 1’-联二萘-2, 2’-二胺-3, 5-二叔丁基水杨醛希夫碱; L2:二((R)-联二萘-2, 2’-二羟基-3-亚胺甲基)-二甘醇二胺希夫碱;L3:二((+)-(R)-1, 1’-联二萘-2, 2’-二羟基-3-亚甲胺基)-1, 2-环己二胺希夫碱;L4:(1R, 2R)-环己二亚氨甲基-吡啶希夫碱;L5:二((+)-(R, R, R, R,)-1, 1’-联二萘-2, 2’-二羟基-3-亚胺甲基)-1, 2-二苯基乙二胺希夫碱。其中配体L2为首次合成,同时得到了L4的晶体并测定了其晶体结构。在配合物的合成中,选用了廉价易得苦味酸盐。首次将苦味酸稀土盐配合物引入不对称催化。二、环氧氯丙烷的水解动力学拆分将合成的5种手性Schiff碱及其苦味酸的稀土配合物用于催化水解动力学拆分环氧氯丙烷。通过对催化剂、反应时间和反应温度的优化,得到了最佳催化条件。在对金属中心的筛选过程中,首次提出了金属离子半径大小对催化反应的影响。本文首次采用配体-金属盐体系直接作为催化剂,简化了实验操作。合成了一种双核金属催化剂,取得了令人满意的立体选择性拆分结果(产率49%,ee值>99%)。稀土配合物用于催化环氧氯丙烷水解动力学拆分为首次应用。三、不对称催化Biginelli反应将合成的5种手性Schiff及其配合物用于催化不对称的Biginelli反应。首先,对反应催化剂、溶剂、反应时间和反应温度优化,得到了最佳的催化Biginelli反应的条件;同时,研究了催化剂的回收效果;对反应的底物进行了扩展:所有产物的产率都达到了令人满意的效果;在水杨醛做底物的Biginelli反应中,产物是一种稠环结构,对其可能发生的反应做了探讨并找到了相关文献依据。把L3引入到反应当中,也得到很好的收率和ee值,这说明设计合成的两种手性催化剂L2和L3都具有不对称催化Biginelli的效果(其中L2催化的反应产率81%,ee值99%,L3催化反应产率80%)。催化剂回收两次效果最佳。我们在不对称催化过程中得到了一种新的物质,由此提出了Biginelli反应的新机理:是一种基于[4+2]环加成的反应。更多还原

【Abstract】 In this paper, five Schiff bases and their rare earth complexes were synthesized and characterized, and the application of the complexes in catalyst for hydrosis kinetic resolution (HKR) of Epichlorohydrin and asymmetric Biginelli reaction were studied.1. Synthesis and characterization of ligands and their complexes The Schiff bases and their rare earth complexes was synthesized and characterized:L~1: (+)-(R)-2,2’-bis(3,5-di-tert-butyl-2-hydroxybenzylideneamino)- 1,1’-binaphthyl;L~2: N,N’-Bis[3-methylene-(R)-1’1’-bi-2-naphthol]-3-oxa-1,5-diaminopentane;L~3: (+)-(R,R,R,R)-Diaminocyclohexane-BINOL-salen;L~4: N,N’-Bis(2-methylenepyridine)-1,2-diaminocyclohexane;L~5: (+)-(R,R,R,R)-Diamino-1,2-diphenylethane-BINOL-salen.The ligand L2 was firstly reported and ligand L4 was characterized by X-ray single crystal diffraction analysis. During the synthesis of the complexes, we chose the lanthanide picrates (Ln=La, Sm, Yb) because of their cheapness and accessibility, which is firstly reported in the asymmetric catalyst.2. Catalyst for hydrosis kinetic resolution (HKR) of EpichlorohydrinThe chiral Schiff base rare earth complexes are applied in catalyst for hydrosis kinetic resolution (HKR) of Epichlorohydrin. We developed the efficient conditions such as catalyst, time and temperature in HKR. The influence of atomic radius to catalystic activity was firstly proposed. The operation of HKR is simplified using the ligand-lanthanide picrate system and obtained the satisfying results (49% yield, 99% e.e.). At the same time, the excellent result (49% yield, >99% e.e.) was obtained by the firstly synthesized heterobimetal complex. Moreover, rare earth complexes using in HKR was firstly reported.3. Catalyst for asymmetric Biginelli reactionThe chiral Schiff bases rare earth complexes were applied in asymmetric catalyst Biginelli reaction. The excellent reaction conditions were obtained by optimizing catalysts, solvents, time and temperature. At the same time, we studied the recycling of catalyst. The excellent results were also obtained by using ligand L3 (yield 80%) in the asymmetric catalyst. Finally, substrates were expanded and excellent results were obtained. It was found that the structure of products was tricycle compounds in which the salicylaldehyde served as substrate.更多还原