【作者】 高飞；

【导师】 夏吾炯；

【作者基本信息】 哈尔滨工业大学 ， 化学工程与技术， 2017， 博士

【摘要】 可见光诱导的有机化学反应因为操作简单、环境污染小、低耗能等优点而引起了科研工作者们的浓厚兴趣。由于烯烃和炔烃两类化合物廉价易得,且能够参与到众多官能团转化反应,而被广泛地应用到有机合成中。烯烃和炔烃的1,2-双官能团化反应能够在一步反应中在双键和三键的两端同时引入不同的官能团,因此在天然产物、药物分子和有机材料等研发中起着重要的作用。近年来,可见光诱导的烯烃和炔烃1,2-双官能团化反应因为条件温和、反应选择性高等优点而得到了化学工作者的广泛关注。本文设计并合成了一系列烯烃及炔烃类衍生物,研究其在可见光诱导条件下的1,2-双官能团化反应,合成了一系列结构多样的喹啉酮、环戊烯并喹啉、苯并菲啶及3-芳酰苯并五元杂环类化合物。含有三氟甲基的有机化合物有着重要的医用价值和实用价值。本文采用Togni’s试剂作为氧化剂及三氟甲基源,fac-Ir(ppy)3作为光催化剂,在可见光诱导的条件下成功地实现了肉桂酰胺类化合物的三氟甲基化反应,制备了各种各样含有三氟甲基的喹啉酮类化合物。而当苯胺的对位含有甲氧基或羟基等官能团时,光照后得到的是含三氟甲基的螺环类化合物。机理研究表明,在可见光诱导的条件下,Togni’s试剂作为一种有效的氧化剂,经过氧化淬灭循环过程生成了三氟甲基自由基,三氟甲基自由基与双键加成,再经过分子内环化反应,最终得到了相应的三氟甲基化产物。此反应的普适性较高,带有给电子或者吸电子取代基的肉桂酰胺类衍生物均能以20%-72%的收率制备相应的三氟甲基化喹啉酮类产物。复杂的多环碳氢化合物作为一种重要的结构单元,在许多天然产物和药物分子中都广泛存在。本文利用1,7-烯炔类化合物作为底物,α-溴代丙二酸二乙酯作为氧化剂,通过可见光氧化还原催化的方法合成了各种环戊烯并喹啉类和苯并菲啶类化合物。机理研究表明,在可见光和光催化剂fac-Ir(ppy)3的作用下,α-溴代丙二酸二乙酯被还原后生成相应的自由基中间体,然后与双键和三键发生分子内的自由基串联反应,形成最终的双环化产物。该合成方法反应产率较高,最高可达95%,对各种官能团都有良好的容忍性,操作简单,一步构建了双环结构,对多环化合物的制备具有着重要的意义。羧酸类衍生物作为一种廉价且储存丰富的化学试剂,被广泛地应用于有机合成中。本文采用含有炔基的羧酸类衍生物作为底物,以空气中氧气作为氧化剂,在可见光诱导的条件下经过分子内脱羧/环化加成/羰基化反应,合成了一系列3-芳酰苯并五元杂环类化合物。研究表明:当底物为α-氨基酸类衍生物时,由于其氧化还原电势较低,在光反应过程中,部分α-氨基酸类底物在没有光催化剂参与的条件下,可直接与空气中的氧气发生单电子转移,得到3-芳酰吲哚类产物;而苯氧乙酸及苯硫乙酸类衍生物在缺乏光催化剂的条件下则无法进行反应。空气中氧气的利用,避免了常见合成方法中需使用一氧化碳等危险原料的缺点,为3-芳酰苯并五元杂环类化合物的合成提供了一条更温和环保、经济节能的途径。更多还原

【Abstract】 Visible-light induced organic reactions have gained much interest from chemists,due to their unique properties,such as simple operation,less environmental pollution and less energy consumption.Since alkenes and alkynes are inexpensive and able to participate in many functional reactions,they are widely used in organic synthesis.1,2-difunctionalization of alkenes or alkynes play an important role in the synthesis of natural products,medicine and organic material,because different functional groups can be simultaneously introduced to the double bond or the triple bond.Notably,owing to mild reaction conditions and high selectivity,visible-light-driven 1,2-difunctionalization of alkenes or alkynes has received considerable attention.In this thesis,a series of alkene and alkyne derivatives were synthesized,and visible-light-driven their 1,2-difunctionalizations were studied to synthesize a variety of quinolinones,cyclopenta[c]quinolines,benzo[j]phenanthridines and 3-acyl heteroaromatic compounds.Compounds containing CF3 group have important medical values and practical values.Herein,a visible-light promoted trifluoromethylation of N-arylcinnamamides was reported.This approach,with Togni’s reagent as oxidant and fac-Ir(ppy)3 as photocatalysis,provides a novel access to synthesize varieties of CF3-containing quinolinones.It is interesting to note that when the para-position of the aniline ring was substituted with a methoxy or hydroxyl group,a CF3-containing spiro product was obtained.Mechanism studies show that under visible light irradiation,Togni’s reagent as oxidant was reductively quenched to generate a stable CF3 radical,which underwent the radical addition of the double bond and intramolecular cyclization to obtain the corresponding CF3-containing products.Moreover,the substrates with electron-donating or-withdrawing substituents were all competent partners in this reaction,and the desired products can be obtained in 20%-72% yields.Complex polycyclic hydrocarbons,as the important structural motifs,can be found in numerous natural products and drug molecules.An efficient approach via photoredox catalysis was disclosed for the synthesis of cyclopenta[c]quinolines or benzo[j]phenanthridines from 1,7-enynes in the presence of α-bromo diethyl malonate as oxidant.A mechanism was proposed that with the help of visible light and photocatalyst fac-Ir(ppy)3,α-bromo diethyl malonate was reducted to generate the corresponding radical intermediate.Then,through radical-triggered tandem additions,the bicyclic products were obtained.Most importantly,this method was featured in up to 95% yield,excellent functional group tolerance and operational simplicity.Moreover,the bicyclic structure can be constructed in one step,which may be of great significance to the preparation of polycyclic compounds.Carboxylic acid derivatives are widely used in organic syntheses as readily available and inexpensive basic chemicals.Utilizing air as oxidant,a photocatalytic process for the easy access to carbonylated heteroaromatic compounds has been established via decarboxylation/ cycloaddition/carbonylation.It is worth noting that when α-amino acid derivatives were employed,the desired product can be obtained in absence of the photocatalyst.However,when phenoxyacetic acids or(phenylthio)acetic acid derivatives were employed,the reactions did not proceed in the absence of either photocatalyst or light.In addition,the oxygen atom of the ketonic carbonyl group originates from air,which averted the use of CO as well as resulted waste.更多还原