以手性亞碸催化劑進行醛的不對稱乙基化反應之研究

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姓名

陳致誠(Chih-Cheng Chen) 查詢紙本館藏

畢業系所

化學學系

論文名稱

以手性亞碸催化劑進行醛的不對稱乙基化反應之研究
(Enantioselective Ethylation of Aldehydes with Diethylzinc Catalyzed by Chiral Sulfoxide)

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摘要(中)

手性亞碸cis-2及trans-2可以透過市售的5-溴基戊酸乙酯為起始物，經過五步驟合成得到。我們應用這些手性亞碸催化劑進行二乙基鋅不對稱加成到苯甲醛反應上。我們也探討了酸添加劑在這個反應中如何促進催化過程。令人驚訝的是，當我們加入50 mol%的4-甲氧基苯甲酸(4-methoxybenzoic acid)時，發現產率和鏡像選擇性有明顯地改善。而且產物的絕對立體化學形式從S變成R。最後，我們也探討不同的芳香族醛進行二乙基鋅不對稱加成反應。

摘要(英)

Chiral sulfoxide cis-2 and trans-2 were synthesized from commercially available 5-bromovalerate through a five-step synthetic route. We demonstrated the application of these chiral sulfoxide catalysts in asymmetric addition of diethylzinc to benzaldehyde and also investigated the promotion of the catalytic process by acid additives. Surprisingly, when we added 50 mol% of 4-methoxybenzoic acid, the yield and enantioselectivity were improved. In addition, the stereochemistry of product changed from S to R, Finally, We also investigated asymmetric addition of diethylzinc to different aromatic aldehydes.

關鍵字(中)

★ 亞碸
★ 不對稱催化
★ 二乙基鋅
★ 乙基化

關鍵字(英)

★ sulfoxide
★ asymmetric catalysis
★ diethylzinc
★ ethylation

論文目次

中文摘要 i
Abstract ii
誌謝 iii
目錄 iv
圖目錄 vi
表目錄 vii
符號說明 viii
第一章緒論 1
1-1 手性亞碸的性質與應用 1
1-2醛的不對稱乙基化反應 9
1-3 實驗動機 16
第二章結果與討論 22
2-1 手性亞碸配位基的製備 22
2-2 醛的不對稱乙基化反應 25
2-2-1催化劑的篩選 25
2-2-2 溶劑的篩選 28
2-2-3 優化苯甲醛不對稱乙基化的反應條件 29
2-2-4 酸添加劑的篩選 31
2-2-5 以不同的芳香族醛進行不對稱乙基化之探討 35
2-2-6 可能的反應機構 38
第三章結論 43
第四章實驗部分 44
4-1 General information 44
4-2 Procedure and spectroscopic data 45
第五章參考文獻 59
附錄 62

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

2015-11-25

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