基于串联反应选择性调控高效合成喹啉衍生物的研究

发布时间：2018-06-18 14:36

  本文选题：喹啉衍生物 + AMBH反应　； 参考：《浙江师范大学》2016年硕士论文

【摘要】：喹啉衍生物是一类十分重要的氮杂环化合物,在自然界广泛存在,由于具有重要的生物活性以及在工业上的广泛应用,使其吸引了大量科学工作者的注意。本文在综述了近年来喹啉合成研究的基础上,从两方面对选择性合成喹啉衍生物进行了研究：(1)仲胺调控化学选择性高效合成喹啉并噻吩衍生物及苯并噻嗪衍生物；(2)奎宁衍生物调控非对映选择性合成具有光学活性的喹啉并硫吡喃衍生物。本课题首先实现了邻异硫氰酸酯肉桂醛和仲胺无催化剂、绿色、高效的串联反应,得到苯并噻嗪类化合物,随后发现L-脯氨酸可以催化邻异硫氰酸酯肉桂醛和溴代试剂的Aza-MBH/Alkylation/Aldol串联反应,选择性生成喹啉并噻吩或喹啉并二氢噻吩类化合物。通过单晶衍射数据分析,确定了产物分子的结构。本课题利用异硫氰酸酯肉桂醛通过分子内AMBH反应芳构化得到2-巯基-3-喹啉甲醛,2-巯基-3-喹啉甲醛与硝基烯烃串联反应,合成了具有3个连续手性碳的喹啉并硫吡喃类化合物。通过条件优化发现奎宁双三氟硫脲Ih和脱甲基丁基醚化奎宁Id两种催化剂能够分别催化该反应,得到优秀的产率、对映选择性和非对映选择性,最重要的是使用两种催化剂得到的产物构型不同,是一对非对映异构体。通过对单晶培养数据分析,确定了两种产物的绝对构型。
[Abstract]:Quinoline derivatives are a kind of very important nitrogen heterocyclic compounds, which exist widely in nature. Because of their important biological activity and wide application in industry, quinoline derivatives have attracted the attention of a large number of scientists. In this paper, based on a review of recent studies on the synthesis of quinoline, the selective synthesis of quinoline derivatives was studied from two aspects: 1) the chemical selective synthesis of quinoline thiophene derivatives and benzothiazine derivatives by secondary amines. Quinine derivatives regulate the enantioselective synthesis of optically active quinolopyran derivatives. In this paper, a series reaction of o-isothiocyanate cinnamaldehyde and secondary amine without catalyst, green and high efficiency was carried out to obtain benzothiazines. It was subsequently found that L-proline could catalyze the Aza-MBH / Alkylation / Aldol series reaction of o-isothiocyanate cinnamaldehyde and brominated reagent to selectively produce quinolino-thiophene or quinoline dihydrothiophene compounds. The structure of the product was determined by single crystal diffraction data. In this paper, 2-mercapto -3-quinolinaldehyde and nitroolefin were synthesized by aromatization of isothiocyanate cinnamaldehyde through intramolecular AMBH reaction. Quinoline and thiopyran compounds with three continuous chiral carbon were synthesized by tandem reaction of 2-mercapto-3-quinolinaldehyde with nitroolefins. It was found that two catalysts, Quinine bisfluorothiourea Ih and demethylated Ding Ji etherifying QuininId, could catalyze the reaction, and obtain excellent yield, enantioselectivity and non-enantioselectivity. The most important thing is that the products obtained by using the two catalysts have different configurations and are a pair of enantiomers. The absolute configuration of the two products was determined by analyzing the data of single crystal culture.
【学位授予单位】：浙江师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626.323

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本文编号：2035825