DDQ介导的非金属交叉偶联反应研究

发布时间：2019-03-15 15:21

【摘要】：交叉脱氢偶联(CDC)反应是指在氧化条件下,未经官能团化的底物直接偶联,从而构建碳碳键或碳杂键的一种方法。此类反应具有更高的原子利用率,更短的实验步骤等优点。为了克服因使用金属催化剂带来的毒性大,费用昂贵及残留物难以消除等缺点,近年来,非金属参与的CDC反应受到越来越多的关注。2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ),作为一种良好的有机氧化试剂,已经在CDC反应中得到了广泛的应用。本论文将以DDQ为氧化剂,研究1,3-二芳基丙烯与具有活性C(sp2)-H的化合物之间的CDC反应,具体内容包括以下两部分:1)DDQ介导的1,3-二芳基丙烯和2-取代-1,4-萘醌及4-羟基香豆素的偶联及成环反应。反应以1,2-二氯乙烷为溶剂,1.2当量DDQ为氧化剂,1,3-二芳基丙烯与2-取代-1,4-萘醌在室温下反应0.5小时,得到烯丙基sp3-C和萘醌sp2-C偶联的产物,具有中等以上的收率。在偶联反应完成后,再加入1.0当量DDQ,则得到相应的成环产物。该偶联及成环反应同样也适用于4-羟基香豆素类化合物。反应生成一系列具有生物活性潜力的2-取代-3-烷基-1,4-萘醌,3-烷基-4-羟基香豆素,吡喃萘醌及吡喃香豆素衍生物。2)DDQ介导的1,3-二苯基丙烯与α-羰基烯酮二硫代缩醛化合物的非金属CDC反应。反应以乙酸乙酯为溶剂,α-羰基烯酮二硫代缩醛与1,3-二苯基丙烯以1:2的投料比,室温反应1小时,得到烯丙基sp3-C和烯酮二硫代缩醛sp2-C偶联的产物,产率良好以上。该方法适用于α-芳(杂)甲酰,乙酰,酯基,酰胺基取代的烯酮二硫代缩醛化合物。在论文中共合成了41个化合物,其结构均经过NMR核磁及ESI高分辨质谱鉴定,论文的研究方法为相应化合物的合成提供了一条简单有效的途径。
[Abstract]:Cross-dehydrogenation-coupling (CDC) reaction is a method of constructing carbon-carbon bonds or heterocarbon bonds by direct coupling of unfunctionalized substrates under oxidation conditions. These reactions have the advantages of higher atomic utilization and shorter experimental steps. In order to overcome the disadvantages of high toxicity, high cost and difficult to eliminate residues caused by the use of metal catalysts, more and more attention has been paid to CDC reactions involving non-metals in recent years. 2,3-dichloro-5,6-dicyanyl-1,4-benzoquinone (DDQ), has been paid more and more attention in recent years. As a good organic oxidation reagent, it has been widely used in CDC reaction. In this paper, DDQ was used as oxidant to study the CDC reaction between 1,3-diarylpropene and compounds with active C (sp2)-H. The main contents are as follows: 1) DDQ-mediated coupling and cyclization of 1,3-diarylpropene and 2-substituted-1,4-naphthoquinone and 4-hydroxy coumarin. In the reaction, 1,2-dichloroethane was used as solvent, 1.2 equivalent DDQ was used as oxidant, 1,3-diarylpropene reacted with 2-substituted-1,4-naphthoquinone at room temperature for 0.5 hours to give allyl sp3-C and naphthoquinone sp2-C coupling products. The yield is above medium. After the coupling reaction was completed, the cyclization product was obtained by adding 1.0eq DDQ,. The coupling and cyclization reactions are also suitable for 4-hydroxy coumarins. A series of 2-substituted-3-alkyl-1,4-naphthoquinone, 3-alkyl-4-hydroxy coumarins with bioactive potential were synthesized. Pyran naphthoquinone and coumarin derivatives. 2) DDQ-mediated non-metallic CDC reaction of 1,3-diphenyl propene with 伪-carbonylenone dithioacetal compounds. Using ethyl acetate as solvent, 伪-carbonyl ketene dithioacetal and 1,3-diphenyl propylene reacted at room temperature for 1 hour to give allyl sp3-C and ketene dithioacetal sp2-C coupling products. The yield is good above. The method is suitable for 伪-aryl (hetero) formyl, acetyl, ester, amide substituted ketene dithioacetal compounds. In this paper, 41 compounds have been synthesized and their structures have been identified by NMR and ESI high resolution mass spectrometry. The method of this paper provides a simple and effective way for the synthesis of the corresponding compounds.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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