臺灣博碩士論文加值系統

因申請專利緣故，資料延後公開
本論文在討論樟腦衍生之掌性β-胺基醇及β-胺基硫醇催化不對稱加成反應之研究。論文共分三部份，第一部份探討一系列β-胺基醇12a–l為催化劑，促進烷基鋅對芳香亞胺的不對稱加成反應。最後以10 mol%的催化劑12a在添加1.8當量的甲醇添加劑條件下，得到60–92%產率的二級芐胺及84–96%的鏡像選擇性。
第二部份探討一系列β-胺基醇31a–42e、43和44，將其應用在不對稱亨利反應。最後以2 mol%的催化劑35e在添加2當量的硼酸三乙酯添加劑條件下，得到21–>99%產率的硝基醇產物及82–96%的鏡像選擇性。値得注意的是，額外添加34 mol%的去離子水，可進一步提升對位-氯苯甲醛之加成物的產率。
第三部份探討β-胺基硫醇30為催化劑，促進重氮乙酸乙酯對苯甲醛的不對稱加成反應，以建立具光學活性的α-重氮-β-羥基酸乙酯，得到92%的產率和66%的鏡像超越值。

因申請專利緣故，資料延後公開
This thesis reports the application of camphor-derived chiral β-amino alcohols and β-amino thiols in asymmetric addition reactions. In the first part, a series of chiral amino alcohols 12a–l has been synthesized and used in the enantioselective addition of dialkylzinc to aromatic aldimines. Application of the optimal chiral ligand 12a (10 mol%) with methanol (1.8 equiv.) as the additive to activate the reaction of aromatic aldimines with diethylzinc and dimethylzinc resulted in high yields (60–92%) and enantioselectivities (84–96% ee).
In the second part, a series of chiral amino alcohols 31e–42e, 43 and 44 has been synthesized and used in asymmetric Henry reaction. Application of the optimal chiral ligand 35e (2 mol%) with triethyl borate (2 equiv.) as the additive to activate the reaction of aldehyde with nitromethane and nitroethane resulted in yields (21–>99%) and enantioselectivities (82–96% ee). Notably, the addition of extra 34 mol% H2O could improve the adduct yield of para-chlorobenzaldehyde.
The third part reports the application of β-amino thiol 30 catalyzed asymmetric addition of ethyl diazoacetate to benzaldehyde to give β-hydroxy a-diazo ester in good yield (92%) and with moderate enantioselectivity (66% ee).

因申請專利緣故，資料延後公開
謝誌 i
中文摘要 iii
英文摘要(abstract) v
目錄 Vii
圖表目錄 ix
縮寫對照表 xv
第一章 緒論 1
第二章 烷基鋅對亞胺的不對稱加成反應 3
2.1 文獻回顧及研究動機 3
2.2 結果與討論 11
2.3 結論 21
第三章 不對稱亨利反應 23
3.1文獻回顧及研究動機 23
3.2 結果與討論 37
3.3 結論 53
第四章 重氮乙酸乙酯對醛的不對稱加成反應 55
4.1文獻回顧及研究動機 55
4.2 結果與討論 60
4.3 結論 66
第五章實驗部份 67
5.1 ㄧ般實驗方法 67
5.2 配位基β-胺基醇12a–12i的合成 68
5.3 甲醇存在下二乙基鋅或二甲基鋅不對稱加成至亞胺的標準步驟 74
5.4 配位基β-胺基醇31–44的合成步驟(亨利反應的配位基) 85
5.5 不對稱亨利反應的標準步驟 128
5.5.1 醛類化合物為液體 128
5.5.2 醛類化合物為固體 128
5.6 配位基β-胺基硫醇30的氫譜及碳譜數據 137
5.7重氮乙酸乙酯對苯甲醛不對稱加成反應的標準步驟 138
參考文獻 139
附錄一化合物之核磁共振光譜圖 145
附錄二高壓液相層析圖 326

因申請專利緣故，資料延後公開
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