过渡金属催化下金属钐介入的偶联反应研究
发布时间：2019-03-05 20:09
【摘要】：本论文主要研究了过渡金属与金属钐构建的催化还原体系在偶联反应中的应用,旨在探究拓展金属钐在有机合成领域的应用范围。第一章是文献综述,分别介绍了钐试剂以及过渡金属催化在有机反应中的研究进展。文中对于二碘化钐、金属钐以及三碘化钐等钐试剂在有机合成中的应用作了详细介绍。过渡金属在有机合成领域的应用甚广,本章只对过渡金属催化碳碳键的形成以及碳杂键的断裂与形成等方面进行了简单综述。第二章主要对二氯化镍催化下金属钐介入的有机卤化物自偶联反应展开了研究。通过一系列实验发现NiCl2/Sm/HMPA构建的催化还原体系可高效实现各种有机卤化物的自偶联反应,并对反应条件进行了优化探讨。在最优的反应条件下,包括苄基卤、芳基卤、杂环卤化物、烯基卤、烷基卤、α-卤代苯乙酮和有机磺酸苯酯等卤代烃或类卤代烃,均能顺利发生自偶联,反应涵盖了Csp3-Csp3与Csp2-Csp2两种类型。结合反应的立体选择性以及一些探究实验对反应机理进行了讨论,并提出了该反应可能的反应机理。该反应使用二氯化镍作为催化剂,在无配体条件下直接将金属钐引入反应,以HMPA作为助剂,不仅操作简单、条件温和,更具有优异的化学选择性与立体选择性。第三章研究了碘化亚铜催化下金属钐介入的有机反应,包括有机卤化物的Barbier型和自偶联反应。首先探究了CuI/Sm介入的卤代烃与羰基化合物的Barbier型反应,发现碘化亚铜与金属钐联用,在不需要其它助剂参与的情况下可顺利实现卤代烃与碳酸酯的亲核加成反应;对反应底物进行了拓展,发现醛、酮、酰氯、酸酐、酯、酰胺等都能够与卤代烃发生反应,分别生成不同系列的化合物。随后又进一步对CuI/Sm介入下芳基卤与DMF的反应进行了详细研究,得到一系列醛;研究同时发现CuI/Sm催化还原体系也能顺利实现卤代烃的自偶联反应,探究了其最优反应条件并初步拓展了反应底物。对反应机理也进行了探索,提出了有机钐中间体的反应历程。目前,进一步的研究工作仍在进行。研究中获得的醛、酮、醇等各系列化合物,均进行了完整的波谱表征,包括1H NMR、13C NMR、IR,相关表征数据和谱图见附录。
[Abstract]:In this paper, the application of transition metal and samarium metal catalytic reduction system in coupling reaction was studied in order to expand the application of samarium metal in organic synthesis. The first chapter is literature review, which introduces the research progress of samarium reagent and transition metal catalysis in organic reaction. The application of samarium diiodide, samarium metal and samarium triiodide in organic synthesis is introduced in detail. Transition metals are widely used in organic synthesis. In this chapter, the formation of carbon bonds catalyzed by transition metals and the fracture and formation of carbon bonds are briefly reviewed. In chapter 2, the self-coupling reaction of samarium metal in organic halide catalyzed by nickel dichloride is studied. Through a series of experiments, it is found that the catalytic reduction system constructed by NiCl2/Sm/HMPA can efficiently realize the self-coupling reaction of all kinds of organic halide, and the reaction conditions are optimized. Under the optimal reaction conditions, halogenated or halogenated hydrocarbons such as benzyl halide, aryl halogen, heterocyclic halides, alkylhalide, 伪-halogenated acetophenone and phenyl organosulfonate can be successfully self-coupled, The reaction covers two types of Csp3-Csp3 and Csp2-Csp2. The reaction mechanism was discussed based on the stereoselectivity of the reaction and some exploratory experiments, and the possible reaction mechanism of the reaction was put forward. In this reaction, nickel dichloride is used as catalyst, samarium metal is directly introduced into the reaction under the condition of no ligand, and HMPA is used as promoter. The reaction is not only simple in operation, mild in condition, but also has excellent chemical selectivity and stereoselectivity. In chapter 3, the organic reactions involving samarium metal catalyzed by cuprous iodide, including Barbier-type and self-coupling reactions of organic halides, are studied. Firstly, the Barbier-type reaction of halogenated hydrocarbons and carbonyl compounds involved by CuI/Sm was investigated. It was found that the nucleophilic addition reaction of halogenated hydrocarbons and carbonates could be successfully realized by the combination of cuprous iodide and samarium metal without the participation of other auxiliaries. It was found that aldehydes, ketones, acyl chloride, anhydrides, esters and amides all reacted with halogenated hydrocarbons to form different series of compounds. Then the reaction of aryl halide with DMF under the intervention of CuI/Sm was studied in detail and a series of aldehydes were obtained. At the same time, it was found that the CuI/Sm catalytic reduction system could successfully realize the self-coupling reaction of halogenated hydrocarbons, and the optimal reaction conditions were explored and the substrate was preliminarily expanded. The reaction mechanism was also explored and the reaction mechanism of organic samarium intermediates was put forward. At present, further research work is still under way. The series of aldehydes, ketones, alcohols and other compounds obtained in this study have been characterized by a complete spectrum, including the relevant data and spectra of 1H NMR,13C NMR,IR, which can be found in the appendix.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
，
本文编号：2435242
[Abstract]:In this paper, the application of transition metal and samarium metal catalytic reduction system in coupling reaction was studied in order to expand the application of samarium metal in organic synthesis. The first chapter is literature review, which introduces the research progress of samarium reagent and transition metal catalysis in organic reaction. The application of samarium diiodide, samarium metal and samarium triiodide in organic synthesis is introduced in detail. Transition metals are widely used in organic synthesis. In this chapter, the formation of carbon bonds catalyzed by transition metals and the fracture and formation of carbon bonds are briefly reviewed. In chapter 2, the self-coupling reaction of samarium metal in organic halide catalyzed by nickel dichloride is studied. Through a series of experiments, it is found that the catalytic reduction system constructed by NiCl2/Sm/HMPA can efficiently realize the self-coupling reaction of all kinds of organic halide, and the reaction conditions are optimized. Under the optimal reaction conditions, halogenated or halogenated hydrocarbons such as benzyl halide, aryl halogen, heterocyclic halides, alkylhalide, 伪-halogenated acetophenone and phenyl organosulfonate can be successfully self-coupled, The reaction covers two types of Csp3-Csp3 and Csp2-Csp2. The reaction mechanism was discussed based on the stereoselectivity of the reaction and some exploratory experiments, and the possible reaction mechanism of the reaction was put forward. In this reaction, nickel dichloride is used as catalyst, samarium metal is directly introduced into the reaction under the condition of no ligand, and HMPA is used as promoter. The reaction is not only simple in operation, mild in condition, but also has excellent chemical selectivity and stereoselectivity. In chapter 3, the organic reactions involving samarium metal catalyzed by cuprous iodide, including Barbier-type and self-coupling reactions of organic halides, are studied. Firstly, the Barbier-type reaction of halogenated hydrocarbons and carbonyl compounds involved by CuI/Sm was investigated. It was found that the nucleophilic addition reaction of halogenated hydrocarbons and carbonates could be successfully realized by the combination of cuprous iodide and samarium metal without the participation of other auxiliaries. It was found that aldehydes, ketones, acyl chloride, anhydrides, esters and amides all reacted with halogenated hydrocarbons to form different series of compounds. Then the reaction of aryl halide with DMF under the intervention of CuI/Sm was studied in detail and a series of aldehydes were obtained. At the same time, it was found that the CuI/Sm catalytic reduction system could successfully realize the self-coupling reaction of halogenated hydrocarbons, and the optimal reaction conditions were explored and the substrate was preliminarily expanded. The reaction mechanism was also explored and the reaction mechanism of organic samarium intermediates was put forward. At present, further research work is still under way. The series of aldehydes, ketones, alcohols and other compounds obtained in this study have been characterized by a complete spectrum, including the relevant data and spectra of 1H NMR,13C NMR,IR, which can be found in the appendix.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
，
本文编号：2435242
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