發(fā)布時間：2019-01-02 15:33

【摘要】：手性有機小分子催化劑在不對稱催化反應(yīng)領(lǐng)域中發(fā)揮著重要的作用。作為手性有機小分子催化劑中的重要一員,手性胍表現(xiàn)出很好的催化性能。基于酒石酸衍生的胍具有原料廉價易得、合成方便、結(jié)構(gòu)易調(diào)變的特點,且具有高催化活性。氟因其獨特的作用被廣泛應(yīng)用到高分子材料、醫(yī)藥學(xué)、化學(xué)、物理學(xué)、生物學(xué)等各領(lǐng)域,并且占據(jù)著重要的地位。不對稱氟化反應(yīng)也是現(xiàn)在人們研究的熱點。將氟原子引入目標(biāo)分子中后,會對分子的物理化學(xué)性質(zhì)產(chǎn)生明顯影響,有時會對藥物分子的藥物活性產(chǎn)生巨大改變。因此,不對稱氟化反應(yīng)在現(xiàn)代研究中有著重要的意義。本文基于本組之前的研究工作,繼續(xù)探究基于酒石酸衍生的手性胍的催化活性。將其應(yīng)用于催化羥吲哚不對稱氟化反應(yīng)中。研究發(fā)現(xiàn),當(dāng)用結(jié)構(gòu)類似的不同胍進行催化時,可以分別得到兩個構(gòu)型相反的氟化產(chǎn)物。通過對催化劑、溶劑、溫度等條件的篩選,確定了最佳反應(yīng)條件,并在最佳反應(yīng)條件下,進行了底物拓展,取得了很好的收率和對映選擇性(高達99%的收率和高達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.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：R914

【共引文獻】

相關(guān)博士學(xué)位論文 前1條

1 鄒立偉;酒石酸衍生的手性胍催化劑的設(shè)計與合成及其在不對稱催化中的應(yīng)用[D];大連理工大學(xué);2014年

相關(guān)碩士學(xué)位論文 前2條

1 宋中太;新型異斯特維醇衍生物的合成及其不對稱催化性能的研究[D];鄭州大學(xué);2014年

2 劉純軍;酒石酸衍生的手性胍催化的N-磺�；鶃啺返牟粚ΨQ環(huán)氧化[D];大連理工大學(xué);2014年

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本文編號：2398677