铜催化含α-氨基腈结构的1,7-烯炔的环化反应的研究

发布时间：2018-10-30 17:07

【摘要】：之前本课题组提出过渡金属催化官能化的α-氨基腈制备含氮杂环的合成方法,提出含有α-氨基腈的烯烃环化特别是功能性双环[4,1,0]烯烃骨架的构建以及其衍生物的合成。但是这类反应中存在着几点局限:其一,当碳碳双键被缺电子基团取代时,这类烯炔环化反应还少见报道;其二,传统过渡金属催化烯炔化合物的环化反应采用的都是铂、金、钯这类的贵金属,增加了工业生产的成本;其三,1,7-烯炔化合物参与的相关报道很少。之前本组已经设计了一种烯烃被拉电子基团取代的氮杂1,7-烯炔化合物在过渡金属铜的催化下发生环化反应获得具有环丙烷结构单元的氮杂二环[4,1,0]庚二烯。以此为前提,本文研究内容主要分为三个部分:(1)由于吖庚因药物具有明显的生物活性,目前已经提出许多用于制备吖庚因杂环的方法,本文发展了一种反应条件简单原子经济性好的方法,通过铜催化含α?氨基腈结构的1,7-烯炔发生环化反应合成4,5-二氢-3H-氮杂七元环吖庚因类化合物。(2)通过偶联-环化反应合成芳环取代的氮杂二环[4,1,0]庚二烯,用碘苯及其取代化合物与含有1,7-烯炔的末端炔烃偶联,进一步发生环化反应。该方法实现了内炔在铜催化条件下环化得到有两个苯环结构的氮杂二环[4,1,0]庚二烯。(3)含氮化合物是一类重要的有机原料,本身具有生理活性。本文通过一锅偶联/环化反应合成氮取代的氮杂二环[4,1,0]庚二烯,用对称叔胺与含有1,7-烯炔的末端炔烃偶联环化构建了含有两个氮原子的环状化合物,本方法简单快捷,节省了后处理的步骤,是一个绿色符合原子经济性的合成方法,但遗憾的是本方法不适用于不对称的胺。
[Abstract]:In the past, our group proposed a method for the synthesis of nitrogen-containing heterocyclic compounds from transition metal catalyzed 伪 -aminonitrile, and proposed that alkenes containing 伪 -aminonitrile, especially functional bicyclic [4U _ 1], be cyclized with 伪 -aminonitrile. Construction of olefins skeleton and synthesis of its derivatives. However, there are several limitations in these reactions: first, when the carbon-carbon double bond is replaced by the electron-deficient group, the cyclization of these alkynes is rarely reported; Second, the traditional transition metal catalyzes the cyclization of alkyne compounds using platinum, gold, palladium and other precious metals, which increases the cost of industrial production. In this paper, we have designed a novel alkenes substituted by electron group for the cyclization of the alkenes with transition metal copper to obtain the heterocyclic [4hl0] heptylenes with cyclopropane structure units. On this premise, this study is mainly divided into three parts: (1) because of the obvious biological activity of acridine, many methods have been proposed for the preparation of acridine heterocycles. In this paper, we have developed a method of simple atomic economy with good reaction conditions, which can be used to catalyze the presence of 伪? The cyclization reaction of 1-butadiene with aminonitrile structure was carried out to synthesize 4o 5-dihydro-3H-azaheptyl compounds. (2) the aromatic ring substituted azacyclohexane was synthesized by coupling cyclization reaction. Iodobenzene and its substituted compounds were coupled to the terminal alkynes containing 1 ~ (7) -alkynes and further cyclization took place. This method has been used to cyclize the alkyne under the condition of copper catalysis to obtain [41H0] heptadiene with two benzene-ring structures. (3) Nitrogen-containing compounds are a kind of important organic raw materials and have physiological activities. In this paper, nitrogen-substituted N-heterobicyclo heptylenes were synthesized by one-pot coupling / cyclization reaction. A cyclic compound containing two nitrogen atoms was synthesized by the coupling cyclization of symmetric tertiary amine with terminal alkynes containing 1-butadiene. The method is simple and fast, saves the post-processing step, and is a green synthesis method which accords with the atom economy, but unfortunately, this method is not suitable for asymmetric amines.
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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