發(fā)布時間：2021-07-30 14:15

　　手性磷酸,作為一種新型的手性布朗斯特酸催化劑,廣泛應(yīng)用于許多有機(jī)不對稱反應(yīng),體現(xiàn)出高效、高對映選擇性的優(yōu)點,已被認(rèn)為是一類優(yōu)勢催化劑。手性磷酸催化劑分子內(nèi)同時含有路易斯堿性位點和布朗斯特酸性位點,可同時活化親電與親核底物,屬于一種雙功能有機(jī)催化劑。由于不同類反應(yīng)（甚至不同底物的同類反應(yīng)）對催化劑的結(jié)構(gòu)都有不同的要求,因此手性磷酸催化劑的結(jié)構(gòu)（尤其是骨架）創(chuàng)新,設(shè)計合成可催化重要有機(jī)反應(yīng)的、更高效的乃至適合天然產(chǎn)物和藥物合成應(yīng)用的手性催化劑,同時根據(jù)手性催化劑能容忍不同官能團(tuán)的特點,設(shè)計發(fā)展不對稱催化的新反應(yīng)、新方法和新策略,仍然是合成化學(xué)家長期的任務(wù)。本文利用課題組發(fā)展的一類基于螺二氫茚骨架的新型手性螺環(huán)磷酸（SPAs）,繼續(xù)發(fā)展手性螺環(huán)磷酸催化劑的新應(yīng)用,研究手性螺環(huán)磷酸不對稱催化合成光學(xué)活性含氮雜環(huán)化合物的新反應(yīng)和新方法。論文的主要內(nèi)容如下:第一章,我們主要概括了手性螺環(huán)磷酸的發(fā)展過程、合成方法、性能特點和在不對稱催化傅克反應(yīng)、費(fèi)歇爾吲哚合成反應(yīng)、去芳化反應(yīng)、環(huán)加成反應(yīng)、插入反應(yīng)、去對稱性反應(yīng)、皮克特—施彭格勒反應(yīng)、多組分反應(yīng)、共軛加成反應(yīng)和其它有機(jī)反應(yīng)中的應(yīng)用現(xiàn)狀,并跟手性聯(lián)萘磷... 

【文章來源】：浙江大學(xué)浙江省 211工程院校 985工程院校 教育部直屬院校

【文章頁數(shù)】：226 頁

【學(xué)位級別】：博士

【文章目錄】：
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
附錄
Publication



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