臺灣博碩士論文加值系統

摘要
　　多種新型的吡類手性噁唑啉雙螯基配體在此論文中設計出且簡單的成功合成出來，並且嘗試運用於二價銅催化不對稱亨利反應中。在二價銅催化的常溫不對稱亨利反應中，可以從不同路易士酸來源的條件，得到位向相反的化合物。實驗中，與Cu(OTf)2形成金屬錯合物催化的常溫不對稱亨利反應得到R位向的化合物 (Yield 97%, 37% ee), Cu(OAc)2形成的金屬錯合物則得到S位向的鄰硝基醇化合物 (Yield 82%, 17% ee)

A series of new pyrazole-containing chiral oxazoline bidentate ligands have been designed, successfully synthesized, and applied to Asymmetric Henry Reaction. Pyrazole-containing chiral oxazoline bidentate ligand has been investigated in catalytic asymmetric Henry reaction of nitroaldol compound with different Lewis acids.The Cu(OTf)2 complex furnished R enantiomer (yield 97%, 37% ee), and Cu(OAc)2 complex afforded S enantiomer (yield 82%, 17% ee).

目錄
摘要 ............................................................................................................. i
英文摘要 .................................................................................................... ii
第一章 緒論 ............................................................................................... 1
1.1 手性分子 ........................................................................................... 2
1.2得到不對稱結構的方法 ................................................................... 4
1.2.1 Racemate resolution ................................................................. 4
1.2.2 Chiral pool ................................................................................ 6
1.2.3 Stereoselective synthesis .......................................................... 7
1.3 亨利反應 ........................................................................................ 10
1.4 金屬催化不對稱反應 .................................................................... 14
1.5 與金屬錯合的配體 ........................................................................ 15
1.6 金屬催化不對稱亨利反應 ............................................................ 16
1.7 其他多種金屬催化不對稱亨利反應 ............................................ 17
1.7.1 鋅金屬催化 .............................................................................. 17
1.7.2 鎘金屬催化 .............................................................................. 18
1.7.3 鈷金屬催化 .............................................................................. 18
1.8噁唑啉 (Oxazoline)系列配體 ........................................................ 20
1.9 希夫鹼 (Schiff base)系列配體 ...................................................... 22
1.10 其他氮氮配體 .............................................................................. 25
1.11. Hybrid ligands .............................................................................. 29
1.12 噁唑啉 (oxazoline) ...................................................................... 31
1.12.1 噁唑啉如何與金屬作用 ........................................................ 32
1.12.2 噁唑啉扮演的角色 ................................................................ 33
第二章 開發新型啉類手性噁唑啉配體 ................................................. 35
2.1 研究動機 ........................................................................................ 35
2.2 配體設計 ........................................................................................ 36
2.3 與噁唑啉搭配的結構 .................................................................... 38
第三章 結果與討論 ................................................................................. 42
3.1配體的合成 ..................................................................................... 42
3.2 噁唑啉的合成 ................................................................................ 43
3.3 雜環化合物的碳氮鍵偶合反應 .................................................... 44
3.3.1 縮減銅催化碳氮鍵偶合反應步驟 .......................................... 52
3.4 銅金屬催化不對稱亨利反應條件 ................................................ 57
3.4.1亨利反應溶劑的選擇 ............................................................... 57
3.4.2中性條件催化不對稱亨利反應 ............................................... 58
3.4.3 二價銅的來源 .......................................................................... 60
3.4.4噁唑啉的手性官能基比較 ....................................................... 65
3.4.5總結 ........................................................................................... 69
3.4.6不同路易士酸造成相異位向選擇性 ....................................... 70
第四章. 結論............................................................................................ 72
第五章. 實驗部分 ................................................................................... 74
5.1儀器及藥品資料 ............................................................................. 74
A. 儀器部分 ..................................................................................... 74
B. 試藥部分 ..................................................................................... 76
溶劑部分 .................................................................................... 77
5.2 製備方法 ........................................................................................ 78
5.2.1 化合物59製備 ........................................................................ 78
5.2.2 化合物60製備 ........................................................................ 79
5.2.3 新式吡類手性噁唑啉配體47-54之合成 ............................... 80
5.2.4 新型吡類手性噁唑啉配體與銅催化不對稱亨利反應 .......... 82
第六章. 參考文獻 ................................................................................... 91

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