亚胺自由基用于构建C-N键的反应研究

发布时间：2018-03-21 10:40

本文选题：亚胺自由基　切入点：氧化环化　出处：《兰州大学》2017年博士论文　论文类型：学位论文

【摘要】：亚胺自由基(Iminiyl Radical)是一类重要的有机反应中间体。亚胺自由基的环化反应可用于含氮杂环化合物的合成。本论文主要探讨了利用亚胺自由基的环化反应合成含氮杂环化合物的新策略。论文包括五部分:第一章简单总结了亚胺自由基的产生方法和反应性,并对亚胺自由基的反应在有机合成中的应用做了简要综述。第二章到第五章介绍了本论文取得的研究结果,具体如下:第二章:非金属条件下,ethyl 2-(N-arylcarbamoyl)-2-iminoacetates可以被氧化成相应的亚胺自由基,亚胺自由基接下来的反应结果取决于反应条件:当用过氧叔丁醇(TBHP)/四丁基碘化铵(TBAI)作氧化剂时,亚胺自由基本位(ipso-)环化生成氮杂螺环己二烯自由基,进而捕获氧气高效生成氮杂螺环己二烯酮产物;而在次氯酸叔丁酯(t-BuOCl)/TBAI/四丁基氯化铵(TBAC)反应体系中,亚胺自由基经分子内邻位(ortho-)环化生成喹喔啉酮产物。第三章:可见光照射下,Ru(phen)3Cl2可以诱导ethyl2-(N-arylcarbamoyl)-2-chloroiminoacetates发生N-Cl键断裂,产生亚胺自由基,后者继而环化,生成喹喔啉酮产物。当用DMF做溶剂时,不加光催化剂反应也可顺利进行。该反应为喹喔啉酮的合成提供了高效的新途径。第四章:可见光条件下,以Zhdankin试剂作为叠氮源,N-arylenamines可经串联叠氮化/分子内C-H胺化反应高效合成喹喔啉类化合物。研究发现,N-arylenamines取代基的性质对反应影响很大:N-aryl-3-arylenamine esters的反应可在非金属条件下进行;N-aryl-3-trifluoromethyl enamine esters反应时则需加入Cu(OAc)2;而要生成2,3-二芳基喹喔啉需用Ru(bpy)3Cl2作光催化剂。第五章:酸性环境中,ethyl 2-(N-arylcarbamoyl)-2-iminoacetates和α-azido-N-arylamides可经分子内傅-克烷基化过程高效合成3-胺基吲哚酮。在Lewis酸BF_3·OEt_2催化下,ethyl 2-(N-arylcarbamoyl)-2-iminoacetates可以发生傅-克烷基化反应,高产率得到3-胺基吲哚酮;α-azido-N-arylamides在Bronsted酸CF_3SO3H作用下经串联的1,2-芳基迁移和傅-克烷基化反应,生成3-芳胺基吲哚酮。
[Abstract]:Imine radical (Iminiyl Radical) is a kind of important organic intermediates. Cyclization reaction of imine radical can be used for the synthesis of nitrogen containing heterocyclic compounds. This thesis mainly discusses the cyclization reaction of imine radical synthesis of nitrogen containing heterocyclic compounds. The new strategy includes five parts: the first chapter is a brief summary the imine radical generating method and reaction, and application of imine radical reactions in organic synthesis are briefly reviewed. The second chapter to the fifth chapter introduces the research results, the paper made as follows: the second chapter: non metal under the condition of ethyl 2- (N-arylcarbamoyl) -2-iminoacetates can be oxidized the corresponding imine radical, reaction results of imine radical next depends on the reaction conditions when using peroxy tert butyl alcohol (TBHP) / four Butyl Ammonium Iodide (TBAI) as oxidant, imine free basic bit (IPSO Ring -) generation Azaspiro Hexadienoic oxygen free radicals, and then capture the efficient generation of Azaspiro dienone products; and in the tert butyl hypochlorite (t-BuOCl) /TBAI/ four Butyl Ammonium Chloride (TBAC) reaction system, imine radical by intramolecular cyclization of ortho (ortho-) formation of Oh, 4-triazol-3-one products. The third chapter: under visible light irradiation, Ru (phen) 3Cl2 ethyl2- (N-arylcarbamoyl) can induce -2-chloroiminoacetates cleavage of N-Cl, which in turn produce imine radical, cyclization, generation of quinoxalone products. When using DMF as solvent, without catalyst reaction the reaction can be carried out smoothly. Provides a new way for the efficient synthesis of quinoxalone. The fourth chapter: under visible light, using Zhdankin reagent as azide source, N-arylenamines series by azide / intramolecular amination of C-H efficient synthesis of quinoxaline compounds. The study found that N-arylenamin Es the properties of the substituents have great influence on the reaction: N-aryl-3-arylenamine esters reaction can be carried out in non metal conditions; N-aryl-3-trifluoromethyl enamine esters reaction is required to join Cu (OAc) 2; and to generate 2,3- two aryl quinoxaline with Ru (bpy) 3Cl2 as photocatalyst. The fifth chapter: in acidic environment, ethyl 2- (N-arylcarbamoyl) -2-iminoacetates and -azido-N-arylamides alpha via intramolecular Friedel crafts alkylation process for efficient synthesis of 3- amino acid Lewis indole ketone. In BF_3 catalyzed by OEt_2, ethyl 2- (N-arylcarbamoyl) -2-iminoacetates can occur Friedel crafts alkylation reaction, high yield 3- amino indole ketone; alpha -azido-N-arylamides acid in Bronsted CF_3SO3H under the action of the 1,2- series of aryl migration and Friedel crafts alkylation reaction, generate 3- arylamino indolin-2-one.

【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.25

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