以手性有機硫催化劑進行不對稱環丙烷化反應並應用於合成吡咯類化合物之研究

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包慧彥(Hui-Yen Pao) 查詢紙本館藏

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化學學系

論文名稱

以手性有機硫催化劑進行不對稱環丙烷化反應並應用於合成吡咯類化合物之研究
((Thiolan-2-yl)diphenylmethanol Benzyl Ether-catalyzed Asymmetric Cyclopropanation and Its Application to the Synthesis of Pyrrole Derivatives)

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摘要(中)

在天然物與藥物中經常出現五員環結構，因此[4+1]環化反應受到了重視。在[4+1]環化反應中，起始物大多為,-不飽和化合物，而硫偶極體(sulfur ylide)與,-不飽和化合物大多進行[2+1]環化反應，故想要利用硫偶極體進行反應，得到五員環產物是有很大的挑戰性。
本研究主要目標為利用實驗室開發的手性硫化物(S)-1作為不對稱環丙烷化反應催化劑，合成三員環化合物，再添加路易士酸進行擴環反應得到五員環吡咯類產物。起始物使用1-氮雜二烯(1-azadienes)，透過2-羥基苯乙酮經過四步驟合成得到。我們也探討反應如何獲得良好的鏡像超越值。

摘要(英)

Five-membered ring is an important structure in natural product and medicinal chemistry, and therefore [4+1] annulation has attracted much attention from organic chemists. While most of the [4+1] annulations were based on ,-unsaturated starting materials, using sulfur ylides and ,-unsaturated compounds to construct five-membered rings still remains a challenge.
The main goal of this thesis is to use sulfur catalyst (S)-1 for developing asymmetric cyclopropanations of 1-azadienes. The resulting cyclopropanes were the treated with Lewis acid for ring-expansion to give five-membered rings. The starting material, 1-azadienes, was synthesized through a 4-step process from 1-(2-hydroxyphenyl)ethan-1-one.

關鍵字(中)

★ 不對稱環丙烷化反應
★ 合成吡咯類化合物
★ 手性有機硫催化劑

關鍵字(英)

★ Asymmetric Cyclopropanation
★ Synthesis of Pyrrole Derivatives
★ chiral sulfur catalyst

論文目次

中文摘要 i
Abstract ii
謝誌 iii
目錄 iv
圖目錄 vi
表目錄 vii
式目錄 viii
縮寫說明 ix
第一章緒論 1
1-1 Johnson-Corey-Chaykovsky反應 1
1-2 使用硫偶極體進行不同的合環反應 3
1-2-1 [4+1]環化反應 4
1-2-2 [4+3]環化反應 7
1-3 實驗動機 9
第二章結果與討論 11
2-1 手性硫化物的製備 11
2-2 1-氮雜二烯的製備 12
2-3 不對稱環丙烷化反應 15
2-3-1 不對稱環丙烷化反應溶劑的篩選 15
2-3-2 以乙腈作為溶劑之鹼的篩選 17
2-3-3 以乙腈作為溶劑之添加劑的篩選 18
2-3-4 以乙腈/水(10/1)作為溶劑之鹼的篩選 20
2-3-5 以乙腈/水(8/1)作為溶劑之添加劑的篩選 21
2-3-6 不對稱環丙烷化反應之溫度的篩選 23
2-3-7 對不同的1-氮雜二烯進行不對稱環丙烷化反應 24
2-4 以路易士酸進行擴環反應 28
2-4-1 路易士酸的篩選 28
2-4-2 對不同的環丙烷進行擴環反應 30
2-5 反應機構的探討 32
第三章結論 35
第四章實驗部分 36
4-1 General information 36
4-2 Procedures and spectroscopic data 37
第五章文獻參考 74
附錄 78

參考文獻

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指導教授

陳榮傑謝發坤(Rong-Jie Chein Fa-Kuen Shieh)

審核日期

2021-1-13

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