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| 研究生： |
陳瑩璇 Chen, Ying-Hsuan |
|---|---|
| 論文名稱： |
外消旋硝基烯丙醇經Rauhut-Currier反應之動力學光學分割 Organocatalytic Kinetic Resolution of Nitroallylic Alcohol via Rauhut-Currier Reaction |
| 指導教授： |
陳焜銘
Chen, Kwun-Min |
| 學位類別： |
碩士 Master |
| 系所名稱： |
化學系 Department of Chemistry |
| 論文出版年： | 2015 |
| 畢業學年度： | 103 |
| 語文別： | 中文 |
| 論文頁數： | 63 |
| 中文關鍵詞： | 動力學光學分割 、Rauhut-Currier 反應 |
| 英文關鍵詞： | Kinetic Resolution, Rauhut-Currier Reaction |
| 論文種類： | 學術論文 |
| 相關次數： | 點閱：135 下載：1 |
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動力學光學分割為簡單有效分離外消旋混合物的方法，而Rauhut-Currier 反應是生成碳-碳鍵的重要方式。本實驗嘗試以丙烯醛與外消旋硝基烯丙醇進行Rauhut-Currier反應，結合動力學光學分割，以去甲氧基奎寧為對掌三級胺催化劑，乙腈為溶劑，於室溫下反應，得到非鏡像異構比為1:1的產物，兩非鏡像異構物之鏡像超越值分別為24%和31%，但回收起始物仍為外消旋混合物；另亦以1,4-二氮雜二環[2.2.2]辛烷與對掌二級胺共催化的方式，使用苯甲酸為添加劑，於-20 oC的溫度下反應，非鏡像異構比最高為4.4:1，但產物與起始物之鏡像選擇性皆不理想。
Kinetic resolution is a conventional and effective way to separate recemates. Rauhut-Currier reaction is an important method to form new carbon-carbon bond. In this study we combine Rauhut-Currier reaction and kinetic resolution. Racemic nitroallylic alcohol and acrolein are catalysted by cupreine in the presence of acetonitrile at ambient temperature. Two diastereomers were obtained and the enantiomeric excess are 24% and 31%, respectively. Recovered starting material is still racemic mixture. On the other way, we use 1,4-diazabicyclo[2.2.2]octane and chiral secondary amine as co-catalyst to optimize the reaction conditions. The reaction use benzoic acid as additive under -20 oC. The diastereomer ratio can be obtained in 4:1, but enantioseletivity of product and recovered starting material are not good.
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