可见光驱动下烯烃（炔烃）的环化及炔烃双官能化反应

发布时间：2018-02-16 00:08

本文关键词： 可见光驱动烯烃炔烃环化反应双官能化　出处：《淮北师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：简单的烯烃、烃炔是普通且常用的有机合成前体,被广泛应用于各种类型的有机合成反应中,例如,加成反应,取代反应及环化反应等。尽管如此在绿色温和反应条件下,实现以简单烯烃或炔烃为原料,一步构建复杂分子仍然是挑战性的课题。近年来可见光驱动的有机反应,做为一种新型高效的合成策略被广泛应用;这种合成方法具有条件温和,易操控的优点。本文主要围绕在可见光作用下,实现有机染料催化烯烃或炔烃为底物的环化反应,以及炔烃与烷基溴代物的双官能化反应,具体如下:1、蓝光驱动下,以10-甲基-9-均三甲苯基吖啶高氯酸盐(Mes-Acr+ClO4 )为催化剂,实现氧气参与的芳基烯烃自身环化反应,直接构建4-芳基四氢萘酮。该合成方法简单温和,高效,且迎合绿色化学概念;反应底物广谱性较好,各种芳基烯烃都可在最佳反应条件下发生自身环化;进一步通过控制实验及顺磁共振测试对机理进行了深入研究。2、蓝光驱动下,以2,4,6-三苯基吡喃盐(2,4,6-triphenylpyrylium tetrafluoroborate)为催化剂,实现了炔烃与腈分子间的[2+2+2]环加成反应,构建多取代吡啶类化合物。同时该环化反应具有良好的区域选择性和底物广谱性,并且通过机理研究证明该环化反应是通过单电子的转移过程实现的。3、绿光驱动下,以曙红-Y(Na2-eosin Y)为催化剂,实现烷基溴代物对芳炔的区域和立体选择性的双官能化反应;该反应实现了在温和和无金属条件下高效地实现烯基溴代物的制备,且对各种取代基具有较好的容忍性。
[Abstract]:Simple olefin, alkyne is a common and commonly used precursor of organic synthesis, which is widely used in various types of organic synthesis reactions, such as addition reaction, substitution reaction and cyclization reaction. It is still a challenging task to construct complex molecules by using simple alkenes or alkynes as raw materials. In recent years, the organic reactions driven by visible light have been widely used as a new and efficient synthesis strategy. This synthetic method has the advantages of mild conditions and easy manipulation. In this paper, the cyclization of alkenes or alkynes catalyzed by organic dyes and the bifunctional reactions of alkyl brominates and alkynes are realized under visible light. The results are as follows: 1, driven by blue light, 4-aryl tetrahydronaphthalone was synthesized by using 10-methyl-9- trimethylphenacridine acridine perchlorate (Mes-Acr ClO4) as catalyst to realize the self-cyclization of aryl olefin with oxygen. The reaction substrate is broad spectrum, and all kinds of aryl olefins can be cyclized under the best reaction conditions. The mechanism was further studied by means of control experiment and paramagnetic resonance test. The [2 2] cycloaddition reaction between alkynes and nitrile molecules was realized by the [2 2 2] cycloaddition reaction between alkynes and nitrile molecules under blue light. Polysubstituted pyridine compounds were constructed. The cyclization reaction has good regioselectivity and broad spectrum of substrate, and the mechanism study shows that the cyclization reaction is realized by single electron transfer process. 3, driven by green light. Using eosin-Yn Na _ 2-eosin Y) as catalyst, the regioselectivity and stereoselectivity of alkyl brominates to arylenes were achieved, which resulted in the efficient preparation of alkenyl brominates under mild and non-metallic conditions. And it has good tolerance to various substituents.
【学位授予单位】：淮北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25;O644.1

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