可见光催化的不饱和烃氧化二聚反应的研究

发布时间：2018-06-20 05:42

本文选题：可见光催化 + 不饱和烃　；参考：《东北师范大学》2017年博士论文

【摘要】：可见光催化是近几年新兴的一个研究领域。它主要利用绿色且广泛存在的可见光作为能源,使用对可见光有较强吸收的光催化剂作为媒介,通过单电子转移或能量转移路径来引发有机化学反应。与传统的紫外光引发的有机反应相比,可见光催化更绿色,更安全,底物的适用范围更广泛,反应也更容易操控。它符合绿色化学和可持续化学的要求,已经成为当代有机化学中热点研究主题之一。本论文从烯烃、炔烃等不饱和烃底物出发,使用空气中的氧气作为绿色氧化剂,利用可见光催化的研究手段,对经由不同机理的不饱和烃氧化二聚反应进行了深入的研究。论文共分五个章节。第一章介绍了可见光催化的研究背景和反应原理,并对基于烯烃自由基阳离子、炔烃自由基阳离子和能量转移机理的可见光催化反应的研究进展做了详细的总结。提出了论文的选题依据。第二章中使用9-均三甲基苯基-10-甲基吖啶高氯酸盐作为光催化剂,研究了以苯乙烯作为底物,经由亲电加成/傅-克环加成/自由基偶联/消除的串联机理合成4-芳基萘衍生物的方法。在反应中使用2-苯基丙二腈作为助催化剂,有效的促进了产物的生成。通过对反应条件的控制,在氧气与氮气的氛围下,分别选择性的合成了4-芳基-1-四氢萘酮和4-芳基-(二氢)萘衍生物。第三章展示了一个从炔烃底物出发,使用绿色的氧气作为终端氧化剂,在温和的条件下高立体选择性的合成1,4-烯二酮的方法。该方法中通过对反应条件的控制,可以选择性的合成顺式或反式烯烃。在顺式合成中可见光具有多重作用:敏化光催化剂、在反应过程中提供能量增加高能态活性中间体的比例和促进产物向顺式的转变。第四章使用共轭二烯酮作为底物,研究了通过“三线态-三线态”能量转移机理实现的分子内与分子间的[2+2]环加成反应,合成了一系列的具有较大环张力的环丁烷和环丁烯类衍生物。并从多个方面对机理进行了验证,证明了能量转移机理的可能性。第五章对可见光催化的研究进行的展望。
[Abstract]:Visible light catalysis is a new research field in recent years. It mainly uses green and widely existing visible light as energy source and uses photocatalyst with strong absorption of visible light as the medium to initiate organic chemical reactions through single electron transfer or energy transfer path. Compared with the traditional UV photo-induced organic reactions, visible photocatalysis is greener and safer, the substrate is more widely used and the reaction is easier to manipulate. It meets the requirements of green chemistry and sustainable chemistry and has become one of the hot research topics in contemporary organic chemistry. Starting from unsaturated hydrocarbon substrates such as olefins and alkynes, using oxygen in air as green oxidant and using visible light catalysis, the oxidation dimerization of unsaturated hydrocarbons by different mechanisms has been studied in this paper. The thesis is divided into five chapters. In the first chapter, the research background and reaction principle of visible light catalysis are introduced, and the research progress of visible light catalytic reaction based on olefin radical cation, alkynes radical cation and energy transfer mechanism is summarized in detail. The basis for selecting the topic of the thesis is put forward. In the second chapter, styrene was used as the substrate, using 9- trimethylphenyl -10-methylacridine perchlorate as photocatalyst. Synthesis of 4-arylnaphthalene derivatives by a series mechanism of electrophilic addition / Friedel-cycloaddition / free radical coupling / elimination. The use of 2-phenylmalonitrile as a cocatalyst can effectively promote the formation of the product. 4-aryl-1-tetrahydronaphthalone and 4-aryl-dihydronaphthalene derivatives were synthesized selectively in the atmosphere of oxygen and nitrogen by controlling the reaction conditions. In chapter 3, a method for the synthesis of 1n 4-enedione with high stereoselectivity under mild conditions using green oxygen as terminal oxidant from alkynes substrate is presented. In this method, cis or trans olefin can be selectively synthesized by controlling the reaction conditions. Visible light has many functions in cis synthesis: sensitized photocatalyst provides energy to increase the proportion of active intermediates in high-energy state and promotes the conversion of products to cis. In chapter 4, using conjugated dienone as substrate, the intramolecular and intermolecular [22] cycloaddition reactions are studied by means of the energy transfer mechanism of "three-wire to three-wire states". A series of cyclobutane and cyclobutene derivatives with high ring tension were synthesized. The mechanism is verified from several aspects and the possibility of energy transfer mechanism is proved. Chapter five looks forward to the research of visible light catalysis.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O643.32;O644.1

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