【摘要】：本論文主要研究了過渡金屬與金屬釤構(gòu)建的催化還原體系在偶聯(lián)反應(yīng)中的應(yīng)用,旨在探究拓展金屬釤在有機(jī)合成領(lǐng)域的應(yīng)用范圍。第一章是文獻(xiàn)綜述,分別介紹了釤試劑以及過渡金屬催化在有機(jī)反應(yīng)中的研究進(jìn)展。文中對(duì)于二碘化釤、金屬釤以及三碘化釤等釤試劑在有機(jī)合成中的應(yīng)用作了詳細(xì)介紹。過渡金屬在有機(jī)合成領(lǐng)域的應(yīng)用甚廣,本章只對(duì)過渡金屬催化碳碳鍵的形成以及碳雜鍵的斷裂與形成等方面進(jìn)行了簡(jiǎn)單綜述。第二章主要對(duì)二氯化鎳催化下金屬釤介入的有機(jī)鹵化物自偶聯(lián)反應(yīng)展開了研究。通過一系列實(shí)驗(yàn)發(fā)現(xiàn)NiCl2/Sm/HMPA構(gòu)建的催化還原體系可高效實(shí)現(xiàn)各種有機(jī)鹵化物的自偶聯(lián)反應(yīng),并對(duì)反應(yīng)條件進(jìn)行了優(yōu)化探討。在最優(yōu)的反應(yīng)條件下,包括芐基鹵、芳基鹵、雜環(huán)鹵化物、烯基鹵、烷基鹵、α-鹵代苯乙酮和有機(jī)磺酸苯酯等鹵代烴或類鹵代烴,均能順利發(fā)生自偶聯(lián),反應(yīng)涵蓋了Csp3-Csp3與Csp2-Csp2兩種類型。結(jié)合反應(yīng)的立體選擇性以及一些探究實(shí)驗(yàn)對(duì)反應(yīng)機(jī)理進(jìn)行了討論,并提出了該反應(yīng)可能的反應(yīng)機(jī)理。該反應(yīng)使用二氯化鎳作為催化劑,在無(wú)配體條件下直接將金屬釤引入反應(yīng),以HMPA作為助劑,不僅操作簡(jiǎn)單、條件溫和,更具有優(yōu)異的化學(xué)選擇性與立體選擇性。第三章研究了碘化亞銅催化下金屬釤介入的有機(jī)反應(yīng),包括有機(jī)鹵化物的Barbier型和自偶聯(lián)反應(yīng)。首先探究了CuI/Sm介入的鹵代烴與羰基化合物的Barbier型反應(yīng),發(fā)現(xiàn)碘化亞銅與金屬釤聯(lián)用,在不需要其它助劑參與的情況下可順利實(shí)現(xiàn)鹵代烴與碳酸酯的親核加成反應(yīng);對(duì)反應(yīng)底物進(jìn)行了拓展,發(fā)現(xiàn)醛、酮、酰氯、酸酐、酯、酰胺等都能夠與鹵代烴發(fā)生反應(yīng),分別生成不同系列的化合物。隨后又進(jìn)一步對(duì)CuI/Sm介入下芳基鹵與DMF的反應(yīng)進(jìn)行了詳細(xì)研究,得到一系列醛;研究同時(shí)發(fā)現(xiàn)CuI/Sm催化還原體系也能順利實(shí)現(xiàn)鹵代烴的自偶聯(lián)反應(yīng),探究了其最優(yōu)反應(yīng)條件并初步拓展了反應(yīng)底物。對(duì)反應(yīng)機(jī)理也進(jìn)行了探索,提出了有機(jī)釤中間體的反應(yīng)歷程。目前,進(jìn)一步的研究工作仍在進(jìn)行。研究中獲得的醛、酮、醇等各系列化合物,均進(jìn)行了完整的波譜表征,包括1H NMR、13C NMR、IR,相關(guān)表征數(shù)據(jù)和譜圖見附錄。
[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, 偽-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.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.251
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本文編號(hào)：2435242