臺灣博碩士論文加值系統

本論文針對新型骨架的掌性含氧籠狀化合物U-2作系統性的研究，分為三部份。
首先，我們利用酵素解析法先得到具有光學活性的起始物(-)-7和(+)-7 (>99% e.e.)，之後經臭氧裂解合成出具有光學活性的含氧籠狀化合物(+)-10和(-)-10，再經由不同取代基的轉換，至終我們可以得到化合物U-2的兩個具光學活性且彼此為鏡像的含氧籠狀化合物(-)-17和(+)-17。
接著，我們從化合物U-2產率的增加，得知在臭氧裂解反應完成後加入酸性樹脂(Amberlyst-15)，能有助於反應中間物24環化地完全。
最後，我們藉著在臭氧裂解反應中控制臭氧通入的當量，可以初步瞭解化合物U-2生成的反應機構。即二環戊二烯上的兩個雙鍵在臭氧裂解反應進行時，norbornene上的雙鍵會被高選擇性地率先裂解開。

Here we have done the systematic research about the novel chiral oxa-cage U-2, and this work can be divided into three parts.
First, we utilize enzymatic resolution to obtain the optical active starting material (-)-7 and (+)-7 (>99%). And after ozonolysis of them, we can afford the optical active oxa-cage compounds (+)-10 and (-)-10. Then we have accomplished several transformations with different substituents on the skeleton. At the end , we obtain two optical active compounds (-)-17 and (+)-17, which are the enantiomeric pair of U-2.
Second, ozonolysis of the dicyclopentadiene, followed by addition of Amberlyst-15, can help the complete cyclization to afford the tetraoxa-cage compound with higher yield.
Finally, by taking control of the amount of entering O3 in ozonolysis, we understand the reaction mechanism from U-1 to U-2 at the first stage. That is , in the progress of ozonolysis, the double bond of norbornene react with ozone with high selectivity.

目 次
中文摘要.....................................................................................................i
英文摘要....................................................................................................ii
謝誌..........................................................................................................iii
目錄...........................................................................................................iv
圖目錄........................................................................................................v
第一章 緒論
1. 碳環籠狀化合物(carbocyclic cage compounds)..................1
2. 雜環籠狀化合物(heterocyclic cage compounds).................2
3. 具光學活性之籠狀化合物.................................................13
第二章 研究構想..................................................................................19
第三章 結果與討論
1. 合成具有光學活性且彼此為鏡像的掌性籠狀化合物.....20
2. 加Amberlyst-15對合成化合物U-2產率的影響.............37
3. 關於二環戊二烯臭氧裂解反應的初步探討.....................42
第四章 結論..........................................................................................48
第五章 實驗..........................................................................................49
第六章 參考文獻..................................................................................66
附錄一（光譜圖）..................................................................................72
簡歷..........................................................................................................91

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