光诱导脱羧酰基化和氧化甲酰化反应

发布时间：2018-06-07 00:47

本文选题：脱羧 + 高碘试剂　；参考：《淮北师范大学》2017年硕士论文

【摘要】：脱羧和氧化酰基化反应是合成甲基酮类农药(医药)中间体和酰胺类生物大分子骨架的有效方法。在光诱导的有机合成反应中,通过能量和单电子的转移形成自由基中间体,进一步发生偶联反应构建目标分子,在过去的几十年中,由于快捷高效和原子经济性的特性成为强大的合成策略而被广泛关注。Rose bengal,eosin Y,Ru(bpy)3Cl2,Ir(ppy)3,吖啶盐等光敏化剂可高效催化脱羧酰基化和氧化酰基化反应。在无光敏化剂参与,可见光诱导条件下,高价碘试剂可催化α-羰基羧酸进行脱羧交叉偶联反应。在以上研究基础上,本论文主要研究工作如下:(1)开发了一种可见光诱导苯基丙酸酯和α-氧代羧酸的脱羧酰基芳基化反应。该反应在没有光敏化剂的存在下,以高价碘试剂(BI-OH)作为催化剂,室温中在蓝光(450 455 nm)照射下,以良好的产率生成相应的香豆素衍生物。该反应条件温和、简单有效,以可见光为驱动力诱导α-氧代羧酸的脱羧酰基化反应。反应体系底物范围广,并以良好的产率得到3-酰基取代香豆素化合物。具有不同位阻(邻位,间位,对位)和电子(富电子和缺电子)效应取代基团的α-酮酸均能发生脱羧酰基化环化反应。(2)无外加光催化剂的条件下,光诱导分子氧实现对N,N-二甲基苯胺的氧化甲酰化,在温和的反应条件下以良好的产率得到相应的甲酰胺。机理实验表明,通过能量转移和单电子转移过程,使1O2和O2·-共同存在于反应中,而且反应过程中起始反应物和产物均起到光敏化剂的作用。N-甲基(N-烷基)苯胺在DME中经(380 385 nm)光照射条件下,氧气可以选择性氧化C(sp3) H键构建酰胺类衍生物。该反应底物广谱性好,N-甲基(N-烷基)仲胺和叔胺都能很好的适应于此反应体系。值得幸运的是,烯基(1,3,3-三甲基-2-亚甲基吲哚啉)、二苯基甲烷和二苯基甲醇可被氧化生成羰基化合物。
[Abstract]:Decarboxylation and oxidative acylation are effective methods for the synthesis of intermediates of methyl ketones and amides. In the photoinduced organic synthesis reaction, free radical intermediates are formed through the transfer of energy and single electron, and further coupling reaction occurs to construct the target molecule. Because of its high efficiency and atomic economy, it has been paid more and more attention to. Rose bengaleosin Yu RubpyN 3Cl2 Irppy3, acridine salt and other Guang Min compounds can efficiently catalyze decarboxylation and oxidative acylation. Under the condition of visible light induction and without the participation of Guang Min, the high valence iodine reagent can catalyze the decarboxylation cross-coupling reaction of 伪 -carbonyl carboxylic acid. Based on the above studies, the main work of this thesis is as follows: 1) A visible light-induced decarboxylation of phenylpropionate and 伪 -oxo-carboxylic acid has been developed. In this reaction, coumarin derivatives were synthesized in a good yield under the irradiation of blue light at room temperature under the irradiation of BI-OH in the presence of no Guang Min. The reaction conditions are mild, simple and effective, and the decarboxylation of 伪 -oxycarboxylic acid is induced by visible light as the driving force. The reaction system has a wide range of substrates and a good yield of 3-acyl substituted coumarin compounds. 伪 -ketoacid with different steric resistance (ortho, m, para-site) and electron (electron-rich and electron-deficient) substituents can occur decarboxylation cyclization reaction. Photoinduced molecular oxygen was used to oxidize N-dimethylaniline, and the corresponding formamide was obtained in a good yield under mild reaction conditions. The mechanism experiment shows that 1O2 and O2-exist together in the reaction through energy transfer and single electron transfer. Moreover, both the starting reactants and the products acted as Guang Min agents. Under the irradiation of DME with 380,385nm), oxygen could selectively oxidize Cnsp3) -H bonds to form amides derivatives. The broad spectrum of the substrate can be well adapted to this reaction system, both the secondary amine and the tertiary amine can be well adapted to the reaction system. Fortunately, alkenyl trimethyl-3-trimethyl-2-methylindoline, diphenyl methane and diphenyl methanol can be oxidized to carbonyl compounds.
【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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