PhIO/Et 3 N·3HF介导的通过烯胺构建氟化2H-氮杂丙烯啶研究

发布时间：2022-02-15 18:03

　　氮杂丙烯啶类化合物是一类非常重要的化合物,同时,也是自然界中存在的最小的一类含氮不饱和的三元环状化合物。这类化合物存在于许多具有生物活性的天然产物中,大部分的氮杂丙烯啶类的化合物是从金色链球菌中提取分离出来的。例如,米勒和其合作者于1970年从链霉菌中分离出azirinomycin,此化合物为含有2H-azirine环的天然产物的第一个例子,发现其对革兰氏阳性和革兰氏阳性菌均表现出广泛的体外抗菌活性。由于氮杂丙烯啶的三元环结构中存在较大的环张力,是许多有机合成中的重要中间体。近些年来,越来越多的化学家们致力于氮杂丙烯啶类化合物的合成方法学研究。目前,合成氮杂丙烯啶类化合物的方法不是特别多,经过查阅文献调研以后,得知已报道的主要合成方法主要有以下几种:（1）经典的Neber反应:以对甲苯磺酸肟为底物,在碱性条件下夺取肟的α位的氢,产生碳负离子,接着碳负离子进攻分子内的氮,随着对甲苯磺酸根的离去,生成2H-氮杂丙烯啶产物。（2）叠氮类化合物通过光解或加热得到2H-氮杂丙烯啶:乙烯基叠氮底物在加热或光照条件下,发生分子内的环合过程,生成2H-氮杂丙烯啶产物。（3）氮杂环丙烷类的衍生物通过消除... 

【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】：140 页

【学位级别】：硕士

【文章目录】：
中文摘要
ABSTRACT
Chapter 1 Research background
    1.1 Introduction
    1.2 The compounds of 2H-azirine existing in nature
    1.3 The methods of synthesizing 2H-azirines
        1.3.1 The classic Neber reaction （route a）
        1.3.2 The azirination of vinyl azides through pyrolysis or photolysis (routeb)
        1.3.3 Through intramolecular elimination or swern oxidation of aziridinederivatives. (route c)
        1.3.4 Intramolecular rearrangement of isoxazole or phosphoisoxazole (routed)
        1.3.5 Intramolecular reactions of carbene with nitriles or nitrene withalkynes. (route e and f)
        1.3.6 Cyclization of β-mono-substituted enamines under the reaction ofhypervalent iodine oxidants. (route g)
        1.3.7 Wolff rearrangement of α-diazo oxime ethers.(route h)
    1.4 Application of 2H-azirine compounds in organic synthesis
        1.4.1 Reactions in which N atoms participates
        1.4.2 Reactions in which N-C2 participates
        1.4.3 Reactions in which C2-C3 participates
        1.4.4 Reactions in which N-C3 participates
    1.5 Important fluorinated drugs
    1.6 Fluorination reaction mediated by hypervalent iodine reagents
    Conclusion
Chapter 2 Project design
    2.1 Introduction
    2.2 Project design and feasibility analysis
    2.3 Research contents
Chapter 3 Results and discussions
    3.1 Introduction
    3.2 The optimization of the reaction conditions
    3.3 Investigation of the scope of substrate application
    3.4 Application of the product for further transformation
    3.5 Reaction mechanism
    3.6 Summary
Chapter 4 Experimental reagents and instruments
    4.1 Source and specification of reagents
    4.2 Analytical instruments and methods
Chapter 5 Experimental sections
    5.1 Preparation of Substrates
    5.2 The Preparation of Iodosylbenzene
    5.3 Preparation of Fluorinated 2H-Azirine 2
Chapter 6 Structure characterization of the prepared compounds
    6.1 Spectral Data of Substrates
    6.2 Spectral Data of Products
References
Notes on publications and participation in scientific research
Appendix 1: Copies of ~1H-NMR,~(13)C-NMR and ~(19)F-NMR Spectra
Appendix 2: X-ray Structure and Data of 2d
Acknowledgement



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