金催化环化反应的理论研究

发布时间：2019-06-19 20:10

【摘要】：本论文中,我们运用密度泛函理论DFT中的M06和B3LYP方法,对如下两个体系进行了理论计算研究。我们研究的目的是提供合理的反应机理,解释实验现象和实验结果,力求为以后相关的实验研究提供一定的理论指导。具体的两个研究体系如下:(1)金催化2-炔基-N-炔丙基苯胺环化反应,提供了用于构建三维二氢吲哚的分步经济方法。在本文第三章中,我们用密度泛函理论中的M06方法更深入研究反应机制和相关的有趣的实验现象。理论研究发现,反应首先经历Au(I)诱导的环化形成吲哚中间体,1,3-炔丙基迁移,并用底物2-炔基-N-炔丙基苯胺(R1)取代生成中间产物丙二烯类物质(P1)。随后,P1通过直接环化转化为最终产物二氢吲哚化合物(P2)。最后,水辅助的氧杂环形成和质子转移产生最终产物。计算的活化自由能表明P1形成比P2形成慢5.9倍,这验证了P1的形成是决速步骤。此外,尽管P1的形成是限速步骤,在几乎所有的底物R1转化为P1之后P2才会生成,我们采用能量跨度模型来合理化解释这个实验作者提出的有趣实验现象。我们发现在形成P1过程中初始易于环化生成的高度稳定的吲哚中间体是这个有趣实验现象产生的关键。在非催化反应中,这种现象是不可能发生的。而某些催化反应中这种现象可以发生。我们的理论研究合理地解释了这种实验现象,从而丰富了物理化学教材中关于连续反应的内容。(2)借助密度泛函理论,我们对金催化氧化双炔化合物环化反应的理论研究及1,6-卡宾迁移之可行性探究(第四章)进行了理论计算研究。经过理论计算研究,我们运用了合理的反应机理解释实验反应。该过程经过更容易的1,2-甲基迁移得到更为稳定的中间体9,然后在经过金的1,2-迁移得到最终产物。同时否定了该反应中的1,6-卡宾迁移。综上,我们对该实验的反应机理进行了理论研究和分析,以检验实验的初步反应机理的可行性,并提供更合理的反应机理来指导未来的研究,为今后该相关研究提供理论指导。
[Abstract]:In this paper, we use the M06 and B3LYP methods in density functional theory (DFT) to study the following two systems. The purpose of our study is to provide a reasonable reaction mechanism, explain the experimental phenomena and experimental results, and strive to provide some theoretical guidance for the related experimental research in the future. The two specific research systems are as follows: (1) Gold catalyzed cyclization of 2-alkynyl-N-propargylphenylamine, which provides a step-by-step economic method for the construction of three-dimensional dihydroindole. In the third chapter of this paper, we use the M06 method in density functional theory to study the reaction mechanism and related interesting experimental phenomena. It was found that the reaction first experienced Au (I)-induced cyclization to form indole intermediate, 1, 3-propargyl migration, and replaced the substrate 2-alkynyl-N-propargylamine (R1) to form intermediate product propanediene (P1). Subsequently, P1 was directly cyclized to the final product dihydroindole compound (P2). Finally, water-assisted oxygen heterocycle formation and proton transfer produce the final product. The calculated activation free energy shows that the formation of P1 is 5.9 times slower than that of P2, which verifies that the formation of P1 is a decisive step. In addition, although the formation of P1 is a rate-limiting step, P2 will not be generated until almost all the substrate R1 is converted to P1. We use the energy span model to rationalize the interesting experimental phenomena proposed by the authors of the experiment. We find that the highly stable indole intermediate which is easy to cyclize in the formation of P1 is the key to the formation of this interesting experimental phenomenon. In non-catalytic reactions, this phenomenon is impossible. This phenomenon can occur in some catalytic reactions. Our theoretical research reasonably explains this experimental phenomenon, thus enriching the content of continuous reactions in physical chemistry textbooks. (2) with the help of density functional theory, we study the theoretical study of cyclization of diacetylene compounds catalyzed by gold oxidation and the feasibility of 1, 6-carbene migration (chapter 4). Through theoretical calculation and research, we use reasonable reaction mechanism to explain the experimental reaction. In this process, a more stable intermediate 9 was obtained by easier migration of 2-methyl, and then the final product was obtained by 1, 2-migration of gold. At the same time, the 1, 6-carbene migration in the reaction was denied. In summary, we have carried on the theoretical research and the analysis to the experiment reaction mechanism, in order to test the feasibility of the preliminary reaction mechanism of the experiment, and provide more reasonable reaction mechanism to guide the future research, and provide the theoretical guidance for the related research in the future.
【学位授予单位】：曲阜师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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