手性螺环磷酸不对称催化合成光学活性含氮杂环化合物的研究

发布时间：2021-07-30 14:15

　　手性磷酸,作为一种新型的手性布朗斯特酸催化剂,广泛应用于许多有机不对称反应,体现出高效、高对映选择性的优点,已被认为是一类优势催化剂。手性磷酸催化剂分子内同时含有路易斯碱性位点和布朗斯特酸性位点,可同时活化亲电与亲核底物,属于一种双功能有机催化剂。由于不同类反应（甚至不同底物的同类反应）对催化剂的结构都有不同的要求,因此手性磷酸催化剂的结构（尤其是骨架）创新,设计合成可催化重要有机反应的、更高效的乃至适合天然产物和药物合成应用的手性催化剂,同时根据手性催化剂能容忍不同官能团的特点,设计发展不对称催化的新反应、新方法和新策略,仍然是合成化学家长期的任务。本文利用课题组发展的一类基于螺二氢茚骨架的新型手性螺环磷酸（SPAs）,继续发展手性螺环磷酸催化剂的新应用,研究手性螺环磷酸不对称催化合成光学活性含氮杂环化合物的新反应和新方法。论文的主要内容如下:第一章,我们主要概括了手性螺环磷酸的发展过程、合成方法、性能特点和在不对称催化傅克反应、费歇尔吲哚合成反应、去芳化反应、环加成反应、插入反应、去对称性反应、皮克特—施彭格勒反应、多组分反应、共轭加成反应和其它有机反应中的应用现状,并跟手性联萘磷... 

【文章来源】：浙江大学浙江省 211工程院校 985工程院校 教育部直属院校

【文章页数】：226 页

【学位级别】：博士

【文章目录】：
摘要
Abstract
Acknowledgement
Chapter.1 Development and application of chiral spirocyclic phosphoric acids in asymmetriccatalysis
    1.1 Introduction
    1.2 Synthesis of SPAs
    1.3 SPAs in asymmetric catalysis
        1.3.1 Friedel- Crafts reactions
        1.3.2 Fischer indole reaction
        1.3.3 Cycloaddition Reaction
        1.3.4 Insertion reactions
        1.3.5 Desymmetrization reactions
        1.3.6 Dearomatization reaction
        1.3.7 Multi-Component reaction
        1.3.8 Pictet-Spengler reaction
        1.3.9 Conjugated addition reactions
        1.3.10 Miscellaneous reactions
    1.4 Conclusion and outlook
    1.5 References
Chapter.2 Organocatalytic asymmetric synthesis of benzazepinoindole derivatives withtrifluoromethylated quaternary stereocenters by chiral phosphoric acid catalysis
    2.1 Introduction
    2.2 Synthesis of trifluoromethyl dihydrobenzoazepinoindoles
    2.3 Optimization of reaction conditions
    2.4 Scope of trifluoromethyl dihydrobenzoazepinoindoles with pyrroles
    2.5 Scope of trifluoromethyl dihydrobenzoazepinoindoles with indoles
    2.6 Plausible mechanism for aza-Friedel-Craft reaction
    2.7 Conclusion
    2.8 Experimental section
        2.8.1 Reagent and instruments
        2.8.2 General procedure for the Enantioselective aza-Friedel-Crafts Reaction with pyrroles orindoles
        2.8.3 Characterization of compounds
    2.9 Refernces
Chapter.3 Organocatalyzed Asymmetric 1,6-Addition Reaction for theConstruction of Unprotected 3,3'-Disubstituted Oxindole Containing Quaternary Stereogeniccenter
    3.1 Introduction
    3.2 Optimization of reaction conditions
    3.3 Scope of oxindolo-methoids and indole
    3.4 Reaction of oxindolo-methoids with pyrrole
    3.5 Non-linear effect
    3.6     Graphical Representation
    3.7     Experimental section
        3.7.1 Chemical and reagent
        3.7.2 Procedure for the synthesis of Oxindole methoids
        3.7.3 Procedure for the Asymmetric 1,6-Addition Reaction for theConstruction of Unprotected3,3-Disubstituted Oxindoles
        3.7.4 Characterization of compounds
    3.8 References
Chapter.4 Asymmetric transfer hydrogenation of seven member cyclic aldimines catalyzed bychiral phosphoric acids
    4.1 Introduction
    4.2 Synthesis of substrates 4.1
        4.2.1 General procedure for the synthesis of substrate dibenzoazepines
    4.3 Optimization reaction conditions for catalytic transfer hydrogenation
        4.3.1 Screening of catalysts and additives
        4.3.2 Screening of solvent and tempreture
    4.4 Conclusion
    4.5 Experimental section
        4.5.1 Chemical and reagents
        4.5.2 General procedure for the synthesis of dibezoazepines
    4.6 Characterization of compounds
    4.7 References
附录
Publication



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