基于Donor-Acceptor环丙烷的二氢萘酚与萘的合成方法研究

发布时间：2018-02-24 13:24

本文关键词： 富电子苯酚 D-A环丙烷二氢萘酚萘路易斯酸串联反应　出处：《兰州大学》2017年硕士论文　论文类型：学位论文

【摘要】：高效快速构建复杂分子结构一直是有机合成研究的重要目标,而串联反应被证实为最有效的方法之一,并且在最近得到了快速发展。本论文第一章将D-A环丙烷参与的反应类型作为背景,通过介绍具体的开环反应和环化反应的典型实例做详细说明。第二章详细介绍了D-A环丙烷作为C3合成子与C4合成子参与的反应,以及我们发展的Sc(OTf)3催化D-A环丙烷与富电子苯酚通过串联反应构筑多取代二氢萘酚的反应;第三章首先对有机小分子催化剂参与的双催化体系进行介绍,在双催化体系的反应背景下,然后对我们发展的3,4,5-三甲基苯酚首次作为有机小分子催化剂与路易斯酸共同催化D-A环丙烷串联反应合成萘进行了详细报道。第一章:引言部分我们以D-A环丙烷的结构特性为出发点,概括D-A环丙烷参与的反应类型,对D-A环丙烷从简单的开环反应到不同类型的串联环化反应进行了分类总结,实例证明D-A环丙烷作为重要的合成子可以与其他反应物快速构建复杂的多环多中心分子骨架,其在构筑碳骨架分子方面具有独特的优势,在全合成应用中有巨大潜力。第二章:首先对D-A环丙烷作为C3合成子和C4合成子参与的反应进行详细的归纳总结,突出了D-A环丙烷在合成具有生物活性分子骨架方面上的多功能性。受到D-A环丙烷与富电子芳香族化合物的傅克烷基化的开环反应启发,我们发展了富电子苯酚与D-A环丙烷的傅克开环反应,并基于此开环反应完成了富电子苯酚与D-A环丙烷高效串联合成二氢萘酚反应研究;改善了在合成二氢萘酚类化合物方面的选择性差和效率低等问题。第三章:通过对有机小分子催化剂参与的双催化体系进行总结,具体反应实例证明:不同催化剂优势互补的双催化体系可以为当前的合成挑战提供新的解决方案和思路。基于我们之前的工作,发现了3,4,5-三甲基苯酚可以作为新型有机小分子催化剂参与反应,在路易斯酸活化D-A环丙烷后,3,4,5-三甲基苯酚作为离去基团对D-A环丙烷通过亲核进攻发生傅克烷基化开环反应,串联反应的最后3,4,5-三甲基苯酚离去后合成萘;这种新型有机小分子的首次被报道,机理方面仍然在进一步研究当中。
[Abstract]:Efficient and rapid construction of complex molecular structures has been an important objective of organic synthesis, and tandem reaction has been proved to be one of the most effective methods. In the first chapter of this paper, the type of reaction in which D-A cyclopropane is involved is used as the background. The typical examples of ring-opening reaction and cyclization reaction are introduced in detail. In Chapter 2, the reaction of D-A cyclopropane as C3 synthesizer and C4 synthesizer is introduced in detail. And we developed a series reaction of D-A cyclopropane and electron-rich phenol to form polysubstituted dihydronaphthol. Chapter 3 introduces the double catalytic system of organic small molecule catalyst. Under the background of double catalytic system, The synthesis of naphthalene from D-A cyclopropane by series reaction of D-A cyclopropane with Lewis acid was reported in detail for the first time. Chapter 1: introduction: we use D-A cyclopropane as a catalyst for the synthesis of naphthalene. Structural characteristics as the starting point, The types of reactions in which D-A cyclopropane is involved are summarized, and D-A cyclopropane reactions from simple ring-opening reactions to different types of series cyclization reactions are classified and summarized. It has been proved that D-A cyclopropane, as an important synthesizer, can rapidly construct complex polycyclic polycentric molecular skeleton with other reactants, and that D-A cyclopropane has unique advantages in the construction of carbon skeleton molecules. In chapter 2, the reactions of D-A cyclopropane as C3 synthesizer and C4 synthesizer are summarized in detail. It highlights the versatility of D-A cyclopropane in the synthesis of biologically active molecular frameworks, and is inspired by the ring-opening reaction of D-A cyclopropane with the Fourier alkylation of electron-rich aromatic compounds. We have developed the Fourier ring opening reaction of E-rich phenol and D-A cyclopropane, and based on this ring-opening reaction, we have completed the efficient series synthesis of dihydronaphthol from electron-rich phenol and D-A cyclopropane. The problems of poor selectivity and low efficiency in the synthesis of dihydronaphthalenol compounds were improved. Examples of specific reactions prove that dual catalytic systems with complementary advantages of different catalysts can provide new solutions and ideas for the current synthesis challenges, based on our previous work, It has been found that 3C4N 5- trimethylphenol can be used as a new type of small organic catalyst to participate in the reaction. After Lewis acid activates D-A cyclopropane, the nucleophilic attack of D-A cyclopropane by nucleophilic attack takes place in the ring-opening reaction of D-A cyclopropane by nucleophilic attack, and after activation of D-A cyclopropane by Lewis acid, the nucleophilic reaction of D-A cyclopropane is carried out. Naphthalene was synthesized after the departure of trimethylphenol and the final 3 ~ 4 ~ (4) O _ 4 in series reaction. The mechanism of this novel organic small molecule has been reported for the first time and the mechanism is still in the process of further study.
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O625

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