臺灣博碩士論文加值系統

本論文探討以對掌輔助劑控制立體化學中心的建立，利用以樟腦架構為主的對掌輔助劑衍生之對掌醯胺，進行非鏡像的氮丙啶合成反應，生成具有非鏡像選擇性的氮丙啶。對掌輔助劑的製備以 (S)-樟腦酮菘酸 (ketopinic acid) 為起始物，經三步合成步驟所得，總產率在 74% 以上，對掌輔助劑的分子結構由 1H 與 13C NMR 圖譜鑑定，其絕對立體化學結構由 X-ray 單晶繞射解析確定。所衍生的α,β-不飽和醯胺先以過溴化溴口比啶及三乙基胺進行溴化取代，再與苯乙基胺反應，得到所需之氮丙啶的非鏡像超越值達 60% de，產物之立體化學結構由 X-ray 單晶繞射確定。

Camphor-derived chiral auxiliary camphor pyrazolidinone were prepared and used for asymmetric aziridination. Camphor pyrazolidinone was prepared from the known (S)-ketopinic acid in 3 steps in a total of 74% yield. The structure and absolute stereochemistry of the chiral auxiliary was assigned unambiguously by 1H, 13C NMR spectrum and X-ray crystallographic analysis. The derived N-enoyl pyrazolidinone was reacted with pyridinium hydrobromide perbromide and triethyl amine, then reacted with benzyl amine to obtain desired aziridine in 60% de.

謝誌
中文摘要 .................................................. 3
英文摘要 .................................................. 4
壹、設計並合成以樟腦為基本架構之對掌輔助劑
貳、對掌α,β-不飽和醯胺與苯乙基胺之非鏡像氮丙啶合成反應
1. 緒論
1.1. 前言 ................................................. 5
1.2. 對掌合成的方法 ....................................... 5
1.3. 樟腦衍生物在有機對掌合成上的應用 ..................... 6
1.4. 對掌輔助劑的設計與合成 ............................... 8
1.5. 氮丙啶合成反應 ....................................... 12
2. 結果與討論 ............................................. 17
2.1 設計並合成以樟腦為基本架構之對掌輔助劑 ................ 17
2.2 對掌α,β-不飽和醯胺之非鏡像環丙烷合成反應 .............. 19
2.3 對掌α,β-不飽和醯胺之丙烯基加成反應 .................... 21
2.4 對掌α,β-不飽和醯胺之三氯甲烷加成反應 .................. 22
2.5 對掌α,β-不飽和醯胺之非鏡像 [3+2] 反應 ................. 23
2.6 對掌α,β-不飽和醯胺之非鏡像環丙烷合成反應 .............. 24
3. 實驗步驟及光譜數據 ..................................... 26
4. 參考資料 ............................................... 36
附錄1. 1H 及13C-NMR 圖譜 .................................. 37
附錄2. 質譜圖 ............................................. 63
附錄3. X-ray單晶繞射結構解析 .............................. 74

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