α-重氮芳酮参与的烯胺酮和N-取代异吲哚-1,3-二酮衍生物的合成研究

发布时间：2018-05-14 21:49

本文选题：重氮化合物 + 烯胺酮　；参考：《江苏师范大学》2017年硕士论文

【摘要】：重氮化合物在有机合成中是一类高活性的合成子,在金属或非金属催化下,原位脱去氮气,转化为高活性的金属卡宾或卡宾中间体,能够与适当的亲核试剂作用,生成一些重要的功能有机分子。它不仅能够参与含氮化合物的合成,也能够进行去重氮化串联反应,实现官能团的转化。因此,在近几年来的研究中,成为有机合成化学领域的研究焦点之一。本文以α-重氮芳酮为关键底物,用其与不同的反应试剂进行反应,通过去重氮化官能团转化,合成结构多样的含氮氧的有机小分子,最大限度地使起始原料转化为目标分子,避免了反应中间体的分离,充分体现了此类反应的原子经济性、合成高效性和环境友好性。本论文由以下四部分组成:第一部分介绍了重氮化合物的性质特征及其进行去重氮化构建C-X键的方法。详细地描述了近几年来化学工作者对此底物展开的一系列研究,包括不同金属催化下卡宾插入的交叉偶联反应和自由基反应,为本文提供了选题依据,意义,创新点和研究方法。第二部分发展了芳甲酰重氮和芳乙炔,芳胺三组分原料在铑/铜的协同催化下的偶联反应,合成了具有高立体选择性的(Z)-N-芳基烯胺酮。该反应过程涉及铑卡宾的原位形成与转金属化、插入迁移和亲核加成等过程,构建了C-N和C-C键。该反应具有优秀的(Z)-选择性,这是分子内的氢键造成的。第三部分发展了一类新型的自由基诱导的三组分反应。该反应以简单易得的原料N,N-二甲基苯胺、N-羟基邻苯二甲酰亚胺与ɑ-重氮芳酮为原料,在醋酸碘苯为自由基引发剂,在室温下进行自由基引发的去重氮化的三组分反应,合成未见文献报道的α-氨基氧基-β-氨基酮,即异吲哚1,3-二酮衍生物。通过实施控制实验证实此转化过程涉及自由基机理。该反应在无金属催化条件下进行,一步实现C-C和C-O键的构建,同时完成了C(sp3)-H的官能团化。第四部分介绍α-重氮芳酮在醋酸碘苯介导下与两分子的N-羟基邻苯二甲酰亚胺反应,在室温下进行自由基引发的去重氮化的三组分反应,合成了一系列结构多样的双异吲哚1,3-二酮衍生物。用N-羟基丁二酰亚胺拓展上述反应,发现此反应底物也能适用于目前的自由基引发的串联反应,提供了一系列的双吡咯烷2,5-二酮衍生物。控制实验证实该反应过程同样也涉及自由基历程。所有合成的产物结构均经核磁共振谱、红外光谱以及高分辨质谱等表征,部分产物结构经单晶X-衍射进一步确证。
[Abstract]:In organic synthesis, diazo compounds are a kind of highly active synthesizers, which, under the catalysis of metal or non-metal, remove nitrogen in situ and convert to highly active metal carbene or carbene intermediates, which can interact with appropriate nucleophilic reagents. Some important functional organic molecules are produced. It can not only take part in the synthesis of nitrogen-containing compounds, but also can carry out the series reaction of dediazotization to realize the conversion of functional groups. Therefore, in recent years, the research has become one of the focuses in the field of organic synthesis chemistry. In this paper, 伪 -diazo aromatic ketones were used as the key substrates to react with different reaction reagents. By the deazotization of functional groups, small organic molecules containing nitrogen and oxygen with various structures were synthesized to maximize the conversion of starting materials into target molecules. The separation of reaction intermediates is avoided, and the atom economy, synthesis efficiency and environmental friendliness of such reactions are fully demonstrated. This paper is composed of four parts: the first part introduces the properties of diazo compounds and the method of deazotization to construct C-X bond. This paper describes in detail a series of studies on this substrate carried out by chemical workers in recent years, including the cross-coupling reaction and free radical reaction of carbene insertion catalyzed by different metals, which provides the basis and significance for this paper. Innovation and research methods. In the second part, the coupling reaction of aryl diazo and aryl acetylene and aromatic amines was developed under the synergistic catalysis of rhodium and copper, and the high stereoselectivity of azo-N-aryl enamine was synthesized. The reaction involves in situ formation and transformation of rhodium carbene, insertion migration and nucleophilic addition. C-N and C-C bonds were constructed. This reaction has excellent selectivity, which is caused by intramolecular hydrogen bonding. In the third part, a new type of free radical-induced three-component reaction is developed. In this reaction, three components of diazotization initiated by free radical at room temperature were carried out by using simple and easy raw materials, N- N- dimethylaniline-N-hydroxy phthalimide and diazo-aromatic ketone as raw materials and iodobenzene acetate as free radical initiator. The synthesis of 伪-aminoxy-尾-amino ketone, I. e., isoindoline 1 and 3-dione derivatives, has not been reported in the literature. The mechanism of free radical involved in the conversion process was confirmed by the control experiment. The reaction was carried out under the condition of no metal catalysis, C-C and C-O bonds were constructed in one step, and the functionalization of C(sp3)-H was completed at the same time. In the fourth part, the reaction of 伪 -diazo aryl ketone with N-hydroxyphthalimide is introduced, which is mediated by iodobenzene acetate, and three components of diazotization initiated by free radical are carried out at room temperature. A series of diisoindole 1-3-diketone derivatives with various structures were synthesized. N- hydroxysuccinimide was used to expand the above reactions. It was found that the substrate could also be used in the series reactions initiated by free radicals and a series of derivatives of dipyrrolidine 2o 5-dione were provided. The control experiment confirmed that the reaction process also involved the free radical process. The structures of all the synthesized products were characterized by NMR, IR and high resolution mass spectrometry, and some of the structures were further confirmed by single crystal X-ray diffraction.
【学位授予单位】：江苏师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.3

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