XJIPC OpenIR  > 资源化学研究室
Thesis Advisor卢崇道、刘波
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline有机化学
Keyword2-乙酰基-6-三甲基硅基苯基三氟甲磺酸酯 3-乙酰基苯炔前体 胺基化 亲核加成反应
Other Abstract

密旋霉素在生物化学和药物方面具有重要的应用价值。近年来,密旋霉素的合成受到了化学家的广泛关注。密旋霉素核心结构——环戊烷C-3 位上具有间取代的氨基苯乙酮的结构。此结构可以通过密旋霉素结构中的氨基环戊糖醇与3-乙酰基苯炔发生亲核加成反应合成。经典的胺与卤代芳烃的偶联是通过过渡金属的催化实现的。此反应存在反应条件苛刻、官能团兼容性差、底物适用范围窄等缺点,以及多官能团、多手性中心的氨基环戊糖醇结构的复杂性,导致其与卤代芳烃在过渡金属催化下构建密旋霉素C-3 位置上间取代的氨基苯乙酮的结构存在一定的困难。因此,本论文的主要任务是:(1)合成能在温和条件下生成3-乙酰基苯炔的前体2-乙酰基-6-三甲基硅基苯基三氟甲磺酸酯。(2)对3-乙酰基进行官能团的修饰,通过电子效应和位阻效应的控制,使胺选择性的对其间位亲核加成。(3)研究2-乙酰基-6-三甲基硅基苯基三氟甲磺酸酯在氟离子的作用下生成的3-乙酰基苯炔与胺的亲核加成反应。本论文以邻三甲基硅基苯酚为原料合成了2-乙酰基-6-三甲基硅基苯基三氟甲磺酸酯并对其官能团进行了修饰;2-乙酰基-6-三甲基硅基苯基三氟甲磺酸酯及其衍生物与胺反应得到中等收率的间位产物。此研究内容对于天然产物密旋霉素C-3 位置上间取代的氨基苯乙酮的结构构建具有潜在的应用价值。

Since pactamycin has important application values in biochemistry and medicine, its synthesis has received extensive attention of chemists in recent years. The core structure of pactamycin is cyclopentane, and its C-3 has the structure of meta-amino acetophenone. This structure can be generated from nucleophilic addition reactions between 3- acetyl benzyne and aminocyclopentitol of pactamycin. The classic coupling between amines and halogenated armotic compounds were catalyzed by transition metals. However, there are many drawbacks for the reaction, such as, the harsh reaction conditions, poor compatibility of the functional groups and narrow scope of the substrates. Moreover, the complex structure of aminocyclopentit- ol leads that it is rather difficult to get meta-acetophenone at C-3 of pactamycin through the reaction between aminocyclopentitol and halogenated armotic compounds catalyzed by transitional metals Therefore, the main work of this paper is: (1)To synthesize the precursor 2-acetyl-6-((trimethylsilyl)phenyl trifluorometha- nesulfonate which could produce 3-acetyl benzyne under mild conditions. (2)To modify 3 - acetyl, and through controlling the electronic effect and steric effect to realize selective meta- nucleophilic addition of amine to 3-acetyl benzyne. (3)To explore the nucleophilic addition reaction between 3-acetyl benzyne and amine in which 3-acetyl benzyne was generated from 2- acetyl-6-(trimethyl)-phenyl thifluoromethanesulfonate in the presence of F- under mild condition .. 2-Acetyl-6-(trimethylsilyl)phenyl trifluoromethanesulfonate was synthesized fro- m 2-(trimethylsilyl)phenol .And it’s functional group was modified. The nucleophilic addition reaction between 2-Acetyl-6-(trimethylsilyl)phenyl trifluoromethanesulfonate and amines got moderate yield. The research will have potential application values for the structure building of memo- acetophenone at C-3 of natural pactamycin
Document Type学位论文
Recommended Citation
GB/T 7714
孙银蕾. 2-乙酰基-6-三甲基硅基苯基三氟甲磺酸酯的合成及胺对其亲核加成反应的研究[D]. 北京. 中国科学院大学,2013.
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