氧化构建含氮杂环及C-H活化在芳基加成反应中的应用研究

发布时间：2020-12-21 15:52

　　有机合成的策略主要是基于分子中官能团之间的相互转化,或者是具有不同化学活性的结构之间的转化。对反应活性较差的C–H键实现直接官能团化来构建新的C–C键或是C–Hetero键是一类非常具有吸引力的反应类型,这种简单的化学反应能够方便快捷的得到目标化合物,与此同时还可以避免传统合成方法中需要预先安装官能团这一过程。但是,由于这类碳氢键高度稳定,进行此类转换常需要严苛的反应条件,并且区域选择性很差,因此限制了它们在合成复杂有机分子中的应用。虽然,这一目标的实现对研究人员来说是一个巨大的挑战,但是,对于复杂的底物选择性碳氢键官能团化这一极具挑战性的课题仍然引起了越来越多的合成研究人员的兴趣。在这些转化中,引入合适的导向基团来增加反应活性和区域选择性是一个不错的选择,通过利用导向基的电性或者配位能力,加之一些高效催化剂的参与,可以对特定的碳氢键进行直接官能团化的转化,因此可以得到具有高度区域选择性的产品,并且增加了反应的活性。像这类容易修饰和移除的导向基,可以应用在复杂分子的合成中。然而,芳基亲电取代反应作为一种传统的合成策略,芳基化合物进行官能团化转化通常需要严苛的反应条件,并且区域选择性非常... 

【文章来源】：天津大学天津市 211工程院校 985工程院校 教育部直属院校

【文章页数】：220 页

【学位级别】：硕士

【文章目录】：
摘要
abstract
Chapter 1 C–C bond formation via C–H activation mediated by main group and transition metals
    1.1 Introduction
    1.2 Deprotonation by organolithium reagents and formation of new C–C bonds
        1.2.1 Introduction of lithium reagents
        1.2.2 Deprotonation by organolithium reagents on sp C and formation of new C–C bonds
        1.2.3 Deprotonation by organolithium reagents on sp2 C and construction of new C–C bonds
        1.2.4 Deprotonation by organolithium reagents on sp3 C and construction of new C–C bonds
    1.3 Construction new C–C bonds through C–H activation with transition-metal catalysts in aromatic compounds
        1.3.1 C–H arylation
        1.3.2 C–H alkylation
        1.3.3 C–H alkenylation
        1.3.4 C–H acylation and carbonylation
Chapter 2 Review of aromatic heterocyclic compounds synthesis
    2.1 Introduction
    2.2 Aromatic heterocyclic compounds synthesis via transition-metal catalysts
        2.2.1 Ruthenium-catalyzed formation of aromatic heterocyclic compounds
        2.2.2 Iridium-catalyzed formation of aromatic heterocyclic compounds
        2.2.3 Palladium-catalyzed formation of aromatic heterocyclic compounds
        2.2.4 Aromatic heterocyclic compounds synthesis via other transition-metal catalysts
    2.3 Aromatic heterocyclic compounds synthesis without transition-metal catalysts
        2.3.1 Intermolecular coupling reactions without transition-metals
        2.3.2 Intramolecular coupling reactions without transition-metals
    2.4 Our study of external-ligand-free aerobic oxidation of N–and C–containing cyclic systems under Pd-catalyzed conditions
        2.4.1 Introduction
        2.4.2 Designing of project
        2.4.3 The results of experiments and discussions
    2.5 Conclusion of this chapter
Chapter 3 The aryl radical reaction mediated by KOt Bu
    3.1 Introduction of radical reactions
    3.2 Radical chain reactions:innate cycles from precursors to products
    3.3 Inhibitors and side reactions:the stealth chain killers
    3.4 Metals as catalysts
        3.4.1 Titanium catalysis
        3.4.2 Iron catalysis
        3.4.3 Ruthenium catalysis
        3.4.4 Cobalt catalysis
        3.4.5 Palladium catalysis
    3.5 Inorganic compounds as catalysts
        3.5.1 Acid as catalysts in radical reactions
        3.5.2 KOtBu as catalyst in radical reactions
    3.6 Our study of building N-and C-containing cyclic systems under KOt Bu through radical reaction
        3.6.1 Introduction
        3.6.2 Designing of project
        3.6.3 Screening reaction conditions
        3.6.4 The expanding of substrates
        3.6.5 Scale-up experiment
        3.6.6 Mechanism study
        3.6.7 Conclusion of this section
Chapter 4 Alkylation of aryl system with norbornene
    4.1 Introduction of norbornene
    4.2 Designing of project
    4.3 Screening reaction conditions
    4.4 Conclusion of this section
Chapter 5 Transition-metal catalyze C–H activation/annulation process
    5.1 Introduction
    5.2 Transition-metal catalyzed C–H activation process to construct five-membered heterocycle
        5.2.1 Indole syntheses
        5.2.2 Furan syntheses
        5.2.3 Methods of synthesizing isoindolone derivatives mediated by metal catalysts
        5.2.4 Methods of synthesizing phthalides mediated by transition metal catalysts
        5.2.5 Methods of synthesizing indenone derivatives mediated by transition metal catalysts
    5.3 Transition-metal catalyzed C–H activation process to construct six-member ring blocks
        5.3.1 Synthesis of isocoumarins mediated by transition-metals
        5.3.2 Synthesis of quinolones mediated by transition-metals
    5.4 Our study of building annulation indenone structure under Pd-catalyzed conditions
        5.4.1 Background
        5.4.2 Designing of project
        5.4.3 Process of making standard curves
        5.4.4 Screen reaction conditions
        5.4.5 Conclusion of this chapter
Chapter 6 Experimental parts and data
    6.1 Instruments and materials
    6.2 Compounds preparation of external ligand-free aerobic oxidation of N,C-containing cyclic systems under Pd-catalyzed conditions
        6.2.1 Preparation of N-containing heterocycle starting materials
        6.2.2 Preparation of N-containing heterocycle compounds under Pd-catalyzed conditions
        6.2.3 Experimental data
    6.3 Compounds preparation of N,C-containing cyclic systems mediated by KOt Bu
        6.3.1 Preparation of N-containing heterocycle starting materials
        6.3.2 Preparation of N-containing heterocycle compounds under KOt Bu conditions
        6.3.3 Free radical capture experiment
        6.3.4 Control experiment of deprotonation
    6.4 Merry-go-round experiment
    6.5 Preparation of oximes
    6.6 Preparation of2,3-diphenyl-1H-inden-1-one
References
Appendix A part of1H NMR data about some compounds
Publication and participation in scientific research
Acknowledgement



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