臺灣博碩士論文加值系統

有機催化連鎖反應和光學分割結合是很有趣的反應類型。本實驗使用醋酸硝基丙烯酯外消旋混合物和戊二醛，以催化劑50催化，進行SN2’-Michael共軛加成-脫去連鎖反應，得到高立體選擇性四取代基環戊烯衍生物(高達96% ee 和12:1 dr)。回收反應性較低的起始物，同樣得到高光學純度(高達99% ee)。在文獻上，此反應是第一次利用不對稱有機催化經由SN2’-Michael共軛加成-脫去連鎖反應，合成高選擇性環戊烯衍生物，並且得到光學分割效率(s)高達143。

The combination of organocatalytic cascade reaction and kinetic resolution is conceptually new in organocatalytic reaction. Treatment of racemic nitroallylic acetates 87 with glutaraldehyde 90 in the presence of a catalyst 50 to give tetrasubstituted cyclopentenes 118 with high to excellent stereoselectivities (up to 96% ee and 12:1 dr) via sequential SN2'-Michael process. The less reactive enantiomeric substrates were generally recovered with good to excellent optical purities (up to 99% ee). This is the first organocatalytic process for the synthesis of functionalized cyclopentenes with excellent stereoselectivities via an SN2′-Michael conjugate addition-elimination process. The selectivity factors (s) for the reaction ranged from 50 - 143.

第一章 導論 .......................................................1
1-1 前言 ........................................................1
1-2 有機催化劑的發展與應用 .......................................3
1-3 不對稱胺催化反應 .............................................9
1-4 有機催化劑在連鎖反應的應用 .................................12
1-5 光學分割反應介紹 .........................................17
1-6 研究動機 ...................................................21
第二章 實驗結果與討論 ...........................................22
2-1 不對稱連鎖反應與光學分割 .............................22
2-1-1 有機催化劑製備 ......................................23
2-1-2 起始物nitroallylic acetate 的製備 ........................25
2-1-3 溶劑效應(1) .........................................26
2-1-4 戊二醛之當量數及催化劑量效應.........................28
2-1-5 添加劑效應(1) .......................................29
2-1-6 催化劑篩選 ..........................................32
2-1-7 溶劑效應(2) .........................................34
2-1-8 添加劑效應(2) .......................................36
2-1-9 HPLC光譜分析 ......................................38
2-1-10 取代基效應 ..........................................39
2-2 絕對立體組態鑑定 .........................................41
2-2-1 起始物立體組態鑑定 ..................................41
2-2-2 產物立體組態鑑定 ....................................43
2-3 反應機構探討 .............................................43
2-4 結論 .....................................................46
第三章 實驗部分 .................................................47
3-1 分析儀器及基本實驗操作 ...................................47
3-2 實驗步驟及光譜數據 .......................................49
3-2-1 有機催化劑92製備 ...................................49
3-2-2 起始物nitroallylic acetate 87製備 ........................50
3-2-3 不對稱有機催化連鎖反應及光學分割反應之實驗步驟 ....51
3-3 參考文獻 .................................................67
附錄一、 1H-NMR、13C-NMR 光譜 ..................................70

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