發(fā)布時(shí)間：2021-05-20 06:53

　　雜環(huán)化合物在自然界中廣泛存在。由于其在藥物結(jié)構(gòu)中被廣泛應(yīng)用,吸引了科學(xué)界的很多注意,用以開發(fā)新的方法學(xué)來合成雜環(huán)化合物。在這些研究中,包含重氮化合物的反應(yīng)是構(gòu)建多種具有生物活性的雜環(huán)化合物的有力工具。通過含卡賓中間體的過渡金屬催化模式,已經(jīng)開發(fā)出了一系列方法來合成雜環(huán),尤其是多組分反應(yīng),為我們提供了一種直接的方式,能夠高立體選擇性的來構(gòu)建結(jié)構(gòu)多樣性的復(fù)雜骨架。這種策略包含了通過金屬卡賓來生成氧鎓葉立德以及兩性離子中間體,在此類中間體形成之后,在親電試劑的存在下,會(huì)通過“延遲質(zhì)子化”來發(fā)生親電捕捉,來生成多種新型的多組分產(chǎn)物。作為我們研究興趣的一部分,我們發(fā)表了多篇通過多種不同重氮化合物作為卡賓前體的多組分反應(yīng)來構(gòu)建雜環(huán)化合物的工作。本論文介紹了一種全新的方法,以重氮酮酸酯與苯胺為底物來構(gòu)建雜環(huán)化合物,與之前報(bào)道的通過親電試劑捕捉氨基葉立德的捕捉方式不同。我們?cè)诜磻?yīng)中引入了包含額外羰基的新型酮酸酯重氮。該策略提供了快速構(gòu)建生物活性雜環(huán)化合物的方法,且原料簡(jiǎn)易可得,反應(yīng)條件溫和。在第二章中,我們介紹了一種以苯胺與重氮酮酸酯為原料,針對(duì)多取代吡咯烷與吲哚的結(jié)構(gòu)多樣性合成。在釕催化劑作用下,苯... 

【文章來源】：華東師范大學(xué)上海市 211工程院校 985工程院校 教育部直屬院校

【文章頁數(shù)】：185 頁

【學(xué)位級(jí)別】：博士

【文章目錄】：
摘要
Abstract
Chapter1 Introduction
    1.1 An Overview of Heterocycles and Their Biological Significance
    1.2 Introduction of Diazo Compounds
        1.2.1 Background
        1.2.2 Stability and Reactivity
    1.3 Synthesis of Heterocycles from Diazo Compounds
        1.3.1 Synthesis of Heterocycles from Diazo Compounds Involving Allene Intermediate
        1.3.2 Synthesis of Heterocycles from Diazo Compounds via Carbene/Alkyne Metathesis
        1.3.3 Synthesis of Heterocycles from Diazo Compounds and Enyne
        1.3.4 Synthesis of Heterocycles from Diazo Compounds via Transition Metal-Catalyzed C-H Functionalization
        1.3.5 Synthesis of Heterocycles via N-H/O-H/C-H Diazo Carbene Insertion
        1.3.6 Synthesis of Heterocycles from Diazo Compounds via Transition Metal-Catalyzed Multicomponent Reaction
    1.4 Research Design and Objective
Chapter2 Diversity-Oriented Synthesis of Multisubstituted Pyrrolidine and Indole from Anilines and Diazopyruvates
    2.1 Research Background
    2.2 Introduction
        2.2.1 Diversity-Oriented Synthesis(DOS)
        2.2.2 Importance of Pyrrolidine and Indole
        2.2.3 Strategies for Construction of Pyrrolidine and Indole
        2.2.4 Design Reaction
    2.3 Initial Investigation and Reaction Optimization
    2.4 Substrate Scope of the Reaction
    2.5 Mechanistic Study
    2.6 Synthetic Application of the Developed Method
    2.7 Proposed Transition State for the Diastereoselectivity
    2.8 Summary
Chapter3 A Facile Synthesis of1,4 Oxazine fromα-Amino Ketones and Diazopyruvates
    3.1 Research Background and Reaction Design
    3.2 Biological Significance of1,4-Oxazine
    3.3 Strategies towards1,4-Oxazine
        3.3.1 Synthesis of1,4-Oxazine via Hydroamination
        3.3.2 Synthesis of1,4-Oxazine via Hydroalkoxylation
        3.3.3 Synthesis of1,4-Oxazine from SnAP Reagents
        3.3.4 Synthesis of1,4-Oxazine from SLAP Reagents
        3.3.5 Synthesis of1,4-Oxazine from Olefin Amine(OLA)Reagents
        3.3.6 Synthesis of1,4-Oxazine from Metal Carbene
        3.3.7 Miscellaneous Strategies
    3.4 Initial Investigation and Reaction Optimization
    3.5 Substrate Scope of the Reaction
    3.6 Possible Mechanism
    3.7 Summary
Chapter4 Conclusion
Chapter5 Experimental
    5.1 General Information
    5.2 Experimental Procedures
        5.2.1 Procedure for the Preparation of Diazopyruvates (2)
        5.2.2 Procedure for the Preparation of Fully-Substituted Pyrrolidine 3 (P-1)
        5.2.3 Procedure for the Preparation of Pyrrolidine 3v
        5.2.4 Procedure for the Preparation of Enol Intermediates (4)
        5.2.5 Procedure for the Synthesis of Substituted Indole 5
        5.2.6 Procedure for the Synthesis of Substituted Pyrrole 6
        5.2.7 Procedure for the Preparation of 1,4-oxazine (3)
        5.2.8 CCK-8 Assay
    5.3 Characterization Data of Products
References
AppendixⅠ: NMR Spectra of Products
AppendixⅡ:X-ray Diffraction analysis
The Author's Resume and Publications
Acknowledgement



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