无金属参与的苯乙烯衍生物分子间胺氟化反应研究

发布时间：2018-06-24 01:48

本文选题：分子间胺氟化反应 + 无金属参与　；参考：《东北师范大学》2017年硕士论文

【摘要】：含氟胺类化合物是一类重要的有机化合物,由于其具有重要的生物和药物活性,被广泛应用于医药和农药方面。因此,含氟胺类化合物的合成引起人们极大的兴趣。烯烃的胺氟化反应是合成含氟胺类化合物最简单、直接的策略之一。目前,过渡金属催化的烯烃分子内胺氟化反应已经取得了很大的成功,合成了各种重要的含有氟原子的含氮杂环化合物。相比之下,烯烃分子间胺氟化反应并不多见。并且,已知的反应通常需要金属催化剂,氮源也需要预先制备,这就使得分之间反应具有很大的局限性。因而,发展一种原料简单易得、简洁、高效的、无金属参与的分子间烯烃胺氟化反应具有重要意义。本论文着重研究了无金属参与的苯乙烯衍生物分子间的胺氟化反应,主要包含以下两个部分:一、以Selectfluor为氧化剂和氟源,廉价易得的三氮唑衍生物作氮源,在温和条件下,成功实现了苯乙烯衍生物分子间胺氟化反应,高效合成了各种含三氮唑的β-氟代苄胺类化合物;二、反应机理的系统研究,通过自由基抑制实验和质谱监测表明该反应首先是烯烃经过单电子氧化形成阳离子自由基中间体,然后发生氟原子转移,最后经过亲核胺化,高选择性的得到胺氟化产物。本论文实现了首例无金属参与的苯乙烯类衍生物分子间三组分胺氟化反应。该反应以Selectfluor为氧化剂和氟源,三氮唑类衍生物为氮源,经过单电子氧化、氟原子转移、亲核胺化,高区域选择性的合成了各种邻位氟代的胺类化合物。该反应条件温和,操作简便,官能团兼容性好,底物廉价易得,为烯烃的双官能团化反应提供了一种新的策略。
[Abstract]:Fluorinated amines are important organic compounds, which are widely used in medicine and pesticides because of their important biological and pharmaceutical activities. Therefore, the synthesis of fluorine-containing compounds has aroused great interest. Amine fluorination of olefins is one of the most simple and direct strategies for the synthesis of fluoroamine compounds. At present, transition metal catalyzed intramolecular amine fluorination of olefins has achieved great success in the synthesis of various important nitrogen-containing heterocyclic compounds containing fluorine atoms. In contrast, the intramolecular fluorination of olefins is rare. Moreover, the known reactions usually require metal catalysts and nitrogen sources need to be prepared in advance, which makes the reactions between fractions have great limitations. Therefore, it is of great significance to develop a simple, efficient and metal-free intermolecular olefin fluorination reaction. In this paper, the amination reaction of styrene derivatives without metal participation was studied. The main contents were as follows: first, using Selectfluor as oxidant and fluorine source, the cheap and easily available triazole derivatives were used as nitrogen sources under mild conditions. The intermolecular fluorination of styrene derivatives was successfully realized, and various 尾 -fluorobenzylamine compounds containing triazole were synthesized efficiently. The free radical inhibition experiments and mass spectrometry showed that the reaction was first the alkenes were oxidized by single electron to form cationic free radical intermediates, then fluorine atoms were transferred, finally nucleophilic amination was used to obtain the fluorinated products with high selectivity. In this paper, the first intermolecular fluorination of styrene derivatives without metal participation was achieved. Using Selectfluor as oxidant and fluorine source, triazole derivatives as nitrogen source, various o-fluorinated amines were synthesized by single electron oxidation, fluorine atom transfer, nucleophilic amination and high region selectivity. The reaction condition is mild, the operation is simple, the functional group compatibility is good, the substrate is cheap and easy to obtain, which provides a new strategy for the bifunctional reaction of olefin.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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