【作者】 刘琼；

【导师】 姬小趁；

【作者基本信息】 湘潭大学 ， 化学， 2020， 硕士

【摘要】 随着人类的发展,人们的科技水平以及工业化水平都在不断提高,而能源危机和环境污染问题却逐渐显现。因此,化学家们把寻求和发展条件温和、绿色高效、选择性良好的合成方法作为新时代追求的目标和前进方向。可见光在自然界中是一种含量丰富的独特资源,它简便易得、没有污染,是一种绿色可再生的能源。近些年来,利用可见光催化有机化学反应成为了合成化学中的研究热点,其中通过光催化与电化学结合以及光催化与传统加热化学结合的有机反应已经在合成领域得到了迅速的发展。含氮杂环类化合物是在农业化学以及药物化学中有着广泛应用的一大类重要的骨架分子。含氮杂环类化合物参与的官能团化反应方法众多,尤其经典的是Minisci反应。利用可见光催化的策略,一大批科学家不断地完善与发展了Minisci反应,实现了杂环的多种官能团化反应。本论文以“可见光激发下芳香醛参与的Minisci反应”作为主题,主要研究了以喹啉和芳香醛为原料的光催化Minisci反应,具体研究内容有如下两个方面:1、发展了一种在可见光激发下无过渡金属催化喹啉与芳香醛的还原偶联反应,实现了喹啉的苄基功能化。该方法首次以喹啉类化合物与芳香醛为原料,利用4Cz IPN作光催化剂,Li Br为添加剂,Tf OH和（Ph O）₂PO₂H作为混酸,合成了一系列苄基化的喹啉类化合物。该方法反应温和,底物适用性广。2、发展了一种在可见光诱导下无过渡金属催化喹啉与芳香醛的直接偶联反应,实现了喹啉的羟甲基功能化。该方法主要利用二苯基喹啉类化合物与芳香醛为原料,4Cz IPN作光催化剂,Li Br为添加剂,Tf OH作为酸,制备了一系列羟甲基化的喹啉类化合物。该反应在无需外部还原剂的条件下得到目标产物,反应条件温和,但在底物适用性和产率上有待进一步提高。更多还原

【Abstract】 With the development of human beings,people’s scientific and technological level and the level of industrialization are constantly improving,while the energy crisis and environmental pollution problems are gradually emerging.Therefore,chemists take the pursuit and development of mild,green,efficient and selective synthetic methods as the goal and direction of the new era.Visible light is a unique and abundant resource in nature.It is easy to obtain and pollution-free.It is a green and renewable energy.In recent years,organic reactions catalyzed by visible light have become a research hotspot in synthetic chemistry,among which organic reactions combining photocatalysis with electrochemistry and photocatalysis with traditional heating chemistry have been developed rapidly in the field of synthesis.Nitrogen-containing heterocycles are an important group of skeleton molecules widely used in agricultural chemistry and pharmaceutical chemistry.The functional reaction of nitrogen-containing heterocyclic compounds was quite extensive,especially the classical Minisci reaction.Using the strategy of visible light catalysis,the Minisci reaction was continuously perfected and developed by a large number of scientists,and the heterogeneous functional groupization of the heterocyclic reaction was realized.This paper took"Minisci reaction of aromatic aldehydes under Visible light excitation"as the theme.The photocatalytic Minisci reaction,using quinoline and aromatic aldehydes as raw materials,was mainly studied in the following two aspects:1.A reduction coupling reaction of quinolines with aromatic aldehydes catalyzed by no transition metal under visible light excitation was developed to realize benzyl functionalization of quinolines.In this method,a series of benzylized quinoline compounds were firstly synthesized from quinoline compounds and aromatic aldehydes,using 4Cz IPN as photocatalyst,Li Br as additive,Tf OH and（Ph O）₂PO₂H as mixed acid.This method has mild reaction and wide applicability.2.A direct coupling reaction between quinolines and aromatic aldehydes without transition metal catalyzed by visible light was developed.A series of hydroxymethylated quinoline compounds were prepared by using diphenylquinoline compounds and aromatic aldehyde as raw materials,4Cz IPN as photocatalyst,Li Br as additive and Tf OH as acid.The target product was obtained without external reducing agent under mild conditions,but the substrate applicability and yield need to be further improved.更多还原