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| 研究生： |
張芸菩 Chang, Yun-Pu |
|---|---|
| 論文名稱： |
多碳環化合物之有機不對稱催化四級連鎖反應 Organocascade Quadruple Reaction：Organocatalytic Enantioselective Synthesis of Functionalized Polycarbocycles |
| 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： | 127 |
| 中文關鍵詞： | 有機不對稱催化反應 、連鎖反應 、多碳環化合物 |
| 英文關鍵詞： | organocatalytic asymmetric reaction, cascade reaction, polycarbocycles |
| 論文種類： | 學術論文 |
| 相關次數： | 點閱：148 下載：2 |
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有機催化反應因有助於環境的永續發展，日漸受到重視。有機不對稱連鎖反應，避免純化中間產物的操作、省去官能基上保護與去保護等繁瑣步驟，降低時間和成本，能夠在一鍋化反應條件中，同時建構出多個碳—碳鍵及立體化學中心。有機連鎖反應與人體中的酵素反應有高度相似性，有機化學家也著手於研究更高等級的連鎖反應，希望藉此高效率的反應策略，應用於天然物的全合成及藥物分子合成。
本實驗以1,3-氫茚雙酮、芳香環醛類及前手性的4-取代環己酮為反應物，以20 mol%的奎寧衍生之硫尿素催化劑、並加入分子篩反應，在25 C的條件下，以三氯甲烷為溶劑，進行有機不對稱四級連鎖反應，反應經Knoevenagel/Michael/aldol/aldol縮合反應，並同時去對稱前手性的4-取代環己烷，有效率地合成出具有螺環結構的多碳環化合物，有不錯的產率、高立體選擇性及高鏡像選擇性。未來期望能利用此反應模式，為耗時之天然物及類固醇藥物的合成，提供新穎的合成策略。
Organocatalysis has been attached much importance as the development of green and sustainable chemistry. Especially, organocatalytic asymmetric cascade/domino reaction, which allows for the efficient construction of sophisticatedly enantioriched product in a one-pot condition. In manipulation, cascade reactions could avoid isolation of intermediates and protection/deprotection steps, it minimize the waste of chemical and reduce the time-consuming of the lengthy sequences. The reaction mode is similar to the mechanism of enzyme, which conduct to convert small molecule into complicated steroids or endocrines in human body. Thus, cascade reactions have attained widespread embrace to perform the total synthesis of natural products or pharmaceutical molecules.
An efficient organocatalytic quadruple cascade reaction among 1,3-indanedione, aryl aldehydes and 4-substituted cyclohexanones has been designed that furnishes spiropolycyclic ring systems in good chemical yields and excellent levels of stereoselectivity（up to >19:1 dr and 99% ee）in the presence of a chiral bifunctional thiourea catalyst and 100 mg 4 Å molecular sieves. The reaction involved in a Knoevenagel/Michael/aldol/aldol condensation sequence with concomitant desymmetrization of prochiral 4-substituted cyclohexanones. Hopefully this synthesis strategy can be utilized in the synthesis of bioactive natural products or steroids systems in the future.
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