酒石酸衍生的手性胍催化的3-取代羟吲哚的不对称氟化反应
发布时间：2019-01-02 15:33
【摘要】：手性有机小分子催化剂在不对称催化反应领域中发挥着重要的作用。作为手性有机小分子催化剂中的重要一员,手性胍表现出很好的催化性能。基于酒石酸衍生的胍具有原料廉价易得、合成方便、结构易调变的特点,且具有高催化活性。氟因其独特的作用被广泛应用到高分子材料、医药学、化学、物理学、生物学等各领域,并且占据着重要的地位。不对称氟化反应也是现在人们研究的热点。将氟原子引入目标分子中后,会对分子的物理化学性质产生明显影响,有时会对药物分子的药物活性产生巨大改变。因此,不对称氟化反应在现代研究中有着重要的意义。本文基于本组之前的研究工作,继续探究基于酒石酸衍生的手性胍的催化活性。将其应用于催化羟吲哚不对称氟化反应中。研究发现,当用结构类似的不同胍进行催化时,可以分别得到两个构型相反的氟化产物。通过对催化剂、溶剂、温度等条件的筛选,确定了最佳反应条件,并在最佳反应条件下,进行了底物拓展,取得了很好的收率和对映选择性(高达99%的收率和高达95%的ee值)。
[Abstract]:Chiral organic small molecule catalysts play an important role in asymmetric catalytic reactions. As an important member of chiral organic small molecule catalysts, chiral guanidine exhibits good catalytic performance. Guanidine derived from tartaric acid is cheap and easy to obtain, easy to synthesize and easy to change in structure, and has high catalytic activity. Fluorine is widely used in polymer materials, medicine, chemistry, physics, biology and other fields because of its unique role, and occupies an important position. Asymmetric fluorination is also a hot research topic. When fluorine atoms are introduced into the target molecule, the physical and chemical properties of the molecule will be obviously affected, and sometimes the drug activity of the drug molecule will be greatly changed. Therefore, asymmetric fluorination is of great significance in modern research. Based on previous studies, the catalytic activity of chiral guanidine derived from tartaric acid was investigated. It was applied to catalyze asymmetric fluorination of hydroxyindoles. It is found that when different guanidine with similar structure is used to catalyze, two fluorinated products with opposite configuration can be obtained respectively. Through the screening of catalyst, solvent, temperature and other conditions, the optimum reaction conditions were determined, and the substrate was expanded under the optimum reaction conditions. Good yield and enantioselectivity (up to 99% yield and 95% ee value) were obtained.
【学位授予单位】：大连理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：R914
本文编号：2398677
[Abstract]:Chiral organic small molecule catalysts play an important role in asymmetric catalytic reactions. As an important member of chiral organic small molecule catalysts, chiral guanidine exhibits good catalytic performance. Guanidine derived from tartaric acid is cheap and easy to obtain, easy to synthesize and easy to change in structure, and has high catalytic activity. Fluorine is widely used in polymer materials, medicine, chemistry, physics, biology and other fields because of its unique role, and occupies an important position. Asymmetric fluorination is also a hot research topic. When fluorine atoms are introduced into the target molecule, the physical and chemical properties of the molecule will be obviously affected, and sometimes the drug activity of the drug molecule will be greatly changed. Therefore, asymmetric fluorination is of great significance in modern research. Based on previous studies, the catalytic activity of chiral guanidine derived from tartaric acid was investigated. It was applied to catalyze asymmetric fluorination of hydroxyindoles. It is found that when different guanidine with similar structure is used to catalyze, two fluorinated products with opposite configuration can be obtained respectively. Through the screening of catalyst, solvent, temperature and other conditions, the optimum reaction conditions were determined, and the substrate was expanded under the optimum reaction conditions. Good yield and enantioselectivity (up to 99% yield and 95% ee value) were obtained.
【学位授予单位】：大连理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：R914
【共引文献】
相关博士学位论文 前1条
1 邹立伟;酒石酸衍生的手性胍催化剂的设计与合成及其在不对称催化中的应用[D];大连理工大学;2014年
相关硕士学位论文 前2条
1 宋中太;新型异斯特维醇衍生物的合成及其不对称催化性能的研究[D];郑州大学;2014年
2 刘纯军;酒石酸衍生的手性胍催化的N-磺酰基亚胺的不对称环氧化[D];大连理工大学;2014年
，本文编号：2398677
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