有机硼化物合成及辅酶NADH模型物的光反应研究

发布时间：2018-07-20 11:21

【摘要】：光催化的有机反应已成为化学研究的热点,其中光催化剂发挥了关键作用。传统的金属光催化剂适用范围广、催化效果好,但毒性高、难回收、稀有金属价格昂贵,所以发展有机光催化剂成为国内外科学家关注的重点。辅酶NADH具有较低的还原电势,可以在光的作用下激发给出电子,具有光催化剂的潜质。我们使用辅酶NADH模型物作为光催化剂,进行光催化的两分子或多分子间有机反应的研究。在本论文中我们介绍了 NADH模型物的研究进展,主要作为还原剂用于有机反应中,近年来国际上对NAD+模型物作为光催化剂的研究引人注目,而作为NAD+的还原态,NADH模型物作为光催化剂将会成为国际社会下一个研究的热点。我们目前的重点是找出合适的底物可以接受NADH模型物在光照下给出的电子,暂时发现了两种:一种是重氮盐,另一种是高价碘摀盐。尤其是高价碘摀盐,在有机合成中的应用吸引了很多科学家的关注。我们也介绍了近几年高价碘摀盐在有机合成中的应用。希望选择合适的高价碘摀盐用于NADH模型物作为催化剂的光反应。我们还介绍了 C(sp3)-CF3和合成喹啉衍生物的研究进展。通过实验我们发现了三氟甲基的高价碘摀盐可以获得辅酶NADH模型物提供的电子,得到三氟甲基自由基参与有机反应。我们对反应的条件进行优化,还拓展了底物。我们在实验中证明重氮盐可以得到NADH提供的电子成为苯基自由基。在乙腈和烯烃或炔烃存在的条件下发生反应,得到喹啉的衍生物。我们对反应进行优化和底物拓展,最后还研究这个反应在药物合成中的应用。我们还研究了有机硼化物的合成。有机硼化物是一种很有用的有机物,在有机合成中有广泛的用途,我们首先介绍合成有机硼化物的研究进展,虽然有很多关于合成有机硼化物的报道,但是这些方法仍有很多缺点,如需要配体、强碱等。我们通过纳米催化剂可以不需要使用任何配体或碱,实现了在非常温和条件下合成有机硼化物,而且官能团的兼容性很好。我们也对使用的纳米金属催化剂进行了表征。
[Abstract]:Photocatalytic organic reaction has become a hot spot in chemical research, among which photocatalyst plays a key role. Traditional metal photocatalysts have a wide range of application and good catalytic effect, but they are highly toxic, difficult to recover and expensive to rare metals. Therefore, the development of organic photocatalysts has become the focus of scientists at home and abroad. Coenzyme nadh has low reduction potential, which can excite and give electrons under the action of light, and has the potential of photocatalyst. We used coenzyme nadh as photocatalyst to study the organic reactions between two or more molecules. In this paper, we introduce the research progress of nadh model compounds, which are mainly used as reducing agents in organic reactions. In recent years, the research on NAD model compounds as photocatalysts has attracted much attention. As a reduced NAD, nadh model as photocatalyst will become the next research hotspot in the international community. Our current focus is to find suitable substrates that can accept electrons from nadh models under light. Two types of diazo salts have been found temporarily: one is diazo salt and the other is high iodide cover salt. In particular, the application of high-price iodide in organic synthesis has attracted the attention of many scientists. We also introduce the application of high-price iodide in organic synthesis in recent years. We hope to select suitable high-valence iodide for the photoreaction of nadh model. The research progress of C (sp3)-CF 3 and the synthesis of quinoline derivatives are also reviewed. Through experiments we found that trifluoromethyl iodide can obtain electrons from coenzyme nadh model and get trifluoromethyl radical to participate in organic reaction. We optimize the reaction conditions and expand the substrate. We have demonstrated in our experiments that diazonium salts can obtain nadh-supplied electrons to form phenyl radicals. In the presence of acetonitrile and alkenes or alkynes, the derivatives of quinoline were obtained. We optimize the reaction and expand the substrate. Finally, we study the application of the reaction in drug synthesis. We also studied the synthesis of organic boride. Organic boride is a very useful organic compound, which has a wide range of applications in organic synthesis. We first introduce the research progress in the synthesis of organic boride, although there are a lot of reports on the synthesis of organic boride. However, these methods still have many disadvantages, such as the need for ligands, strong bases and so on. We can synthesize organic boride under very mild conditions without using any ligands or alkaloids. The functional groups are compatible with each other. The nano-metal catalysts were also characterized.
【学位授予单位】：合肥工业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O627.31;O644.1

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