氮杂环卡宾不对称催化串联反应合成四氢萘并吡喃酮衍生物及分子间Stetter反应研究

发布时间：2019-01-19 11:18

【摘要】：本论文以氮杂环卡宾作为有机小分子催化剂,对不对称催化MichaelMichael-内酯化串联反应和分子间Stetter反应进行了研究。论文包括三部分:第一章本部分对氮杂环卡宾催化醛类化合物生成的酰基阴离子中间体、α,β-不饱和酰基正离子中间体、烯醇式和高烯醇式等价物在有机合成中的应用研究进展进行了综述。第二章使用氮杂环卡宾不对称催化α-溴代-α,β-不饱和醛与2-甲基-3,5-二硝基苯基烯酮的Michael-Michael-内酯化串联反应,以中等产率(最高56%)、高非对映选择性(25:1)和对映选择性(99%ee)合成了含有三个连续手性碳的四氢萘并吡喃酮衍生物。该不对称催化串联反应具有条件温和,立体选择性好的优点,为四氢萘并吡喃酮衍生物的合成提供了新的途径。第三章利用氮杂环卡宾催化2-甲酰基苯基氨基甲酸甲酯与2-氰基-α,β-不饱和酮的分子间Stetter反应,以高非对映选择性(25:1 dr)和较高的产率(最高80%)得到了一系列Stetter反应产物,该类化合物具有合成苯并氮杂卓类衍生物的潜在应用价值。
[Abstract]:In this paper, nitrogen-heterocyclic carbene is used as an organic small molecular catalyst, and the reaction of asymmetric catalysis of Michael-lactonization and the inter-molecule Stetter reaction are studied. The paper includes three parts: the first chapter is a review of the progress of the application in the organic synthesis of the base anion intermediate, the benzene, the p-unsaturated alicyclic cation intermediate, the enolate and the high enolase equivalent produced by the azetidine-catalyzed aldehyde compound in the first part. The second chapter uses the nitrogen heterocyclic carbene to catalyze the Michael-Michael-lactonization of the 2-methyl-3,5-dinitrophenyl ketene in a serial reaction with the Michael-Michael-lactone of the 2-methyl-3,5-dinitrophenyl ketene in a symmetric manner, with a medium yield (up to 56%), high diastereoselectivity (25: 1) and enantioselectivity (99% ee) synthesize a tetrahydro-dihydro-pentanone derivative containing three continuous chiral carbons. The asymmetric catalytic series reaction has the advantages of mild condition and good three-dimensional selectivity, and provides a new way for the synthesis of the tetrahydro-methyl-pentanone derivative. In the third chapter, a series of Stetter reaction products were obtained by the inter-molecule Stetter reaction of 2-methylphenyl-phenylcarbamate and 2-cyanogen-1, 1-unsaturated ketone by using N-heterocyclic carbene, and the high diastereoselectivity (25: 1 dr) and the higher yield (up to 80%) were obtained. The compounds have potential application values for the synthesis of benzodiazepines derivatives.
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

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