發(fā)布時間：2020-12-21 15:52

　　有機合成的策略主要是基于分子中官能團之間的相互轉化,或者是具有不同化學活性的結構之間的轉化。對反應活性較差的C–H鍵實現(xiàn)直接官能團化來構建新的C–C鍵或是C–Hetero鍵是一類非常具有吸引力的反應類型,這種簡單的化學反應能夠方便快捷的得到目標化合物,與此同時還可以避免傳統(tǒng)合成方法中需要預先安裝官能團這一過程。但是,由于這類碳氫鍵高度穩(wěn)定,進行此類轉換常需要嚴苛的反應條件,并且區(qū)域選擇性很差,因此限制了它們在合成復雜有機分子中的應用。雖然,這一目標的實現(xiàn)對研究人員來說是一個巨大的挑戰(zhàn),但是,對于復雜的底物選擇性碳氫鍵官能團化這一極具挑戰(zhàn)性的課題仍然引起了越來越多的合成研究人員的興趣。在這些轉化中,引入合適的導向基團來增加反應活性和區(qū)域選擇性是一個不錯的選擇,通過利用導向基的電性或者配位能力,加之一些高效催化劑的參與,可以對特定的碳氫鍵進行直接官能團化的轉化,因此可以得到具有高度區(qū)域選擇性的產品,并且增加了反應的活性。像這類容易修飾和移除的導向基,可以應用在復雜分子的合成中。然而,芳基親電取代反應作為一種傳統(tǒng)的合成策略,芳基化合物進行官能團化轉化通常需要嚴苛的反應條件,并且區(qū)域選擇性非常... 

【文章來源】：天津大學天津市 211工程院校 985工程院校 教育部直屬院校

【文章頁數(shù)】：220 頁

【學位級別】：碩士

【文章目錄】：
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



本文編號：2930093