钯催化非官能团化卤代芳烃去芳香化反应研究

发布时间：2018-07-10 15:03

本文选题：Pd催化 + 非官能团化卤代芳烃　；参考：《郑州大学》2017年硕士论文

【摘要】：芳香族化合物广泛地存在于大自然中,因其廉价易得且具有多样性的结构,被广泛的运用到科学研究与工业生产中,用于各类化工原料、天然产物以及医药中间体的合成。化学家们对此进行了广泛且深入的研究,其中,以芳香化合物的去芳香化策略来构建复杂分子中的杂环或螺环骨架,是一种有效的手段,引起了化学家们的广泛关注。近年来,去芳香化反应得到了长足的发展,在药物、天然产物以及功能材料的合成中扮演了愈来愈重要的角色,大量关于去芳香化的报道被发表到了国际著名学术期刊。迄今为止在该领域的科学研究,已经较为全面的涵盖了当量试剂参与的去芳香化反应以及过渡金属催化去芳香化反应。催化去芳香化反应以其条件温和且具有良好的底物兼容性而备受科学家的青睐。然而,目前为止的催化去芳香化反应研究多集中在官能团化芳香化合物或杂环底物,鲜有非官能团化芳香化合物的直接去芳香化反应报道。本课题组通过研究发现一种新型的催化去芳香化反应体系,合成了一系列的脱芳构化螺环化合物。通过对催化反应体系的优化,我们筛选出了最优的反应条件:以0.20 mmol1-碘代萘、2.5 equiv.4-辛炔为反应底物,2.5 mol%Pd2(dba)3为催化剂,1.0 equiv.HCOONa为质子源,2.0 equiv.NaOtBu为碱,2 mL甲苯为反应溶剂,置于25 mL Schlenk反应管中氮气气氛保护,在120℃下反应12 h,以85%的分离收率得到目标化合物。为了研究不同官能团对去芳香化反应的影响,我们合成了带有不同取代基团的1-碘代萘衍生物以及杂环、多环卤代物。此外,我们也合成了不同类型的炔烃以研究反应体系对炔烃的容忍性。通过对去芳香化反应体系的研究,我们成功得到了12种非官能团化卤代芳烃的脱芳构化产物,且均已使用高分辨质谱与核磁共振1H与13C表征。该催化去芳香化反应体系可以实现非官能团化卤代芳烃的直接去芳香化,突破了官能团化芳烃的底物限制,具有一定的创新性,丰富了去芳香化策略研究体系,在有机合成方法学中具有较大的研究意义。
[Abstract]:Aromatic compounds are widely distributed in nature. Because of their cheap and diverse structure, they are widely used in scientific research and industrial production and used in the synthesis of various chemical materials, natural products and pharmaceutical intermediates. Chemists have carried out extensive and in-depth studies on this, including aromatic compounds. The aromatization strategy is an effective means to construct the heterocyclic or spiral skeleton of complex molecules, which has attracted wide attention of chemists. In recent years, the reaction of de aromatization has been greatly developed and plays a more and more important role in the synthesis of drugs, natural products and functional materials, and a great deal of reports about aromaticity are reported. The scientific research in this field has so far already covered a comprehensive coverage of the de aromatization reaction of equivalent reagents and transition metal catalyzed de aromatization. Catalytic de aromatization has been favored by scientists for its mild conditions and good substrate compatibility. So far, the research of catalytic dearomatization is mostly concentrated on functional aromatic compounds or heterocyclic substrates, and there are few reports of direct dearomatization of non functional aromatic compounds. Through the optimization of the catalytic reaction system, we screened the optimal reaction conditions: 0.20 mmol1- iodide naphthalene, 2.5 equiv.4- symplecyne as the reaction substrate, 2.5 mol%Pd2 (DBA) 3 as the catalyst, 1 equiv.HCOONa as the proton source, 2 equiv.NaOtBu as the base, 2 mL toluene as the reaction solvent, in the 25 mL Schlenk reaction tube nitrogen atmosphere protection, 120 In order to study the effect of different functional groups on dearomatization, we synthesized 1- iodide naphthalene derivatives with different substituent groups and heterocyclic halogenates with different substituents. In addition, we also synthesized different types of alkynes to study the tolerance to alkynes in the reaction system in order to study the effect of different functional groups on dearomatization reaction at 12 h. Through the study of dearomatization reaction system, we have successfully obtained 12 kinds of dearomatization products of non functional halogenated aromatics, and all have been characterized by high resolution mass spectrometry and nuclear magnetic resonance 1H and 13C. The catalytic dearomatization system can realize direct dearomatization of aromatic halogenated aromatics and break through functional group aromatics The substrate restriction is innovative, enriching the research system of de aromatization strategy, and has great research significance in organic synthesis methodology.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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