本文選題：Baylis-Hillman反應 + 手性誘導�。� 參考：《湘潭大學》2017年碩士論文

【摘要】：Baylis-Hillman反應是一類能高效構(gòu)建碳-碳鍵的三組分反應,其產(chǎn)物具有多個可以進一步轉(zhuǎn)換的官能團,因此該類型反應在有機合成中得以廣泛關(guān)注。近年來,發(fā)展了眾多誘導不對稱Baylis-Hillman反應的體系,針對這些體系中存在的底物選擇范圍窄、反應時間長、對映選擇性低等問題。本論文展開了對手性誘導不對稱Baylis-Hillman反應的方法研究,優(yōu)化了兩類手性誘導下的反應條件,獲得新型、高效的手性誘導體系。1、手性底物的設計合成及在Baylis-Hillman反應中的應用分別以L-薄荷醇、托品醇、右旋冰片、巴豆酸與肉桂酸為原料,設計合成了五類手性活潑烯烴并應用于不對稱Baylis-Hillman反應中,考察了催化劑種類、用量、時間、溫度與溶劑體系對反應的誘導效果的影響。結(jié)果表明:以2-硝基苯甲醛與丙烯酸薄荷醇酯為底物時的Baylis-Hillman反應為模型,反應溶劑為DMF:H2O=9:1,DABCO與底物摩爾比為1:2:2時,20℃下反應36 h時誘導效果最佳,收率達84%,de值達91%;在最優(yōu)反應條件下進行底物拓展,發(fā)現(xiàn)含拉電子基的芳香醛為底物時反應效果較好(收率高達91%,de值高達95%),而供電子基的芳香醛反應效果欠佳;同時考察丙烯酸托品醇酯、丙烯酸冰片酯、肉桂酸薄荷醇酯和巴豆酸薄荷醇酯這四種手性活潑烯烴與硝基苯甲醛的Baylis-Hillman反應,得到較好的結(jié)果;在此基礎上,進一步探究了不對稱反應產(chǎn)物酯水解反應,產(chǎn)物具有較高的立體選擇性。2、手性溶劑的合成及在Baylis-Hillman反應中的應用分別以L-丙氨酸、L-苯丙氨酸、L-脯氨酸與L-組氨酸為原料,合成了十二種氨基酸類離子液體。并將其作為手性溶劑,在普通條件下(即催化劑、底物為非手性)利用溶劑控制誘導不對稱Baylis-Hillman反應。對反應的催化劑種類、用量、手性溶劑及共溶劑、溫度與時間進行優(yōu)化,結(jié)果表明:以2-硝基苯甲醛和丙烯酸甲酯的Baylis-Hillman反應為模型,DABCO與2-硝基苯甲醛和丙烯酸甲酯摩爾比為1:1:6,L-脯氨酸乙酯[BF4-]為手性溶劑,在-10℃下反應36 h,誘導效果最佳,收率達41%,ee值達46%;在最優(yōu)反應條件下,對底物的普適性進行考察,發(fā)現(xiàn)4-硝基苯甲醛為底物時反應效果較好(收率為51%,ee值56%);考察了不同的活潑烯烴在氨基酸類離子液體作為手性溶劑下的Baylis-Hillman反應,得到了較好的結(jié)果。
[Abstract]:Baylis-Hillman reaction is a class of three component reactions that can efficiently construct carbon carbon bonds. The products have many functional groups that can be further converted. Therefore, this type of reaction has been widely concerned in organic synthesis. In recent years, many systems to induce asymmetric Baylis-Hillman reactions have been developed to select the substrates that exist in these systems. The narrow range, long reaction time, low enantioselectivity and low enantioselectivity have been carried out in this paper. The method of asymmetric Baylis-Hillman reaction was studied in this paper. The reaction conditions of two classes of chiral inducers were optimized. A new and efficient chiral induction system.1 was obtained. The design and synthesis of chiral substrates and the application of L- in Baylis-Hillman reaction were respectively Five kinds of chiral active olefins were designed and synthesized from menthol, atropol, dextra, and cinnamic acid as raw materials. In the asymmetric Baylis-Hillman reaction, the effects of the type, dosage, time, temperature and solvent system on the reaction induced by the catalyst were investigated. The results showed that 2- nitrobenzaldehyde and menthol acrylate were used. When the Baylis-Hillman reaction is a model for substrate, the reaction solvent is DMF:H2O=9:1 and the molar ratio of DABCO to substrate is 1:2:2, the reaction is best when the reaction is 36 h at 20 C, the yield is 84%, the de value reaches 91%. Under the optimal reaction conditions, the substrate is expanded and the reaction effect is better when the aromatic aldehyde containing the tensile electron is the substrate (the yield is up to 91%, de The value is up to 95%) and the reaction effect of the aromatic aldehyde for the electronic base is not good. At the same time, the Baylis-Hillman reaction of four kinds of chiral active olefin and nitrobenzaldehyde, such as acrylic acid ester, borneol, cinnamic acid menthol ester, and menthol ester of Croton acid, has been investigated. On the basis of this, the asymmetric reaction is further explored. The product has high stereoselective.2, the synthesis of chiral solvent and the application of Baylis-Hillman in the synthesis of twelve kinds of amino acid ionic liquids, respectively, are L- alanine, L- phenylalanine, L- proline and L- histidine, and are used as chiral solvents under ordinary conditions (catalyst, bottom). Asymmetric Baylis-Hillman reaction was induced by solvent control. The type, dosage, chiral solvent and co solvent of the reaction were used to optimize the temperature and time. The results showed that the Baylis-Hillman reaction of 2- nitrobenzaldehyde and methyl acrylate was the model, and the molar ratio of DABCO to 2- nitrobenzaldehyde and methyl acrylate was 1: 1:6, L- proline ethyl [BF4-] is a chiral solvent, and the reaction is 36 h at -10 C. The yield is best, the yield is 41%, the EE value reaches 46%. Under the optimal reaction conditions, the universality of the substrate is investigated and the reaction effect is better when 4- nitrobenzaldehyde is the substrate (the yield is 51%, EE value 56%), and the different active olefin in the amino acid ions is investigated. As a Baylis-Hillman reaction under chiral solvents, the liquid obtained good results.
【學位授予單位】：湘潭大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.25

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1 張鎖江;姚曉倩;劉曉敏;王金泉;;離子液體構(gòu)效關(guān)系及應用[J];化學進展;2009年11期

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本文編號：1916599