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| 研究生： |
陳家玄 Chen, Jia-Xuan |
|---|---|
| 論文名稱： |
催化1,3-二烯烴進行[2+2]-亞硝基芳香烴環化加成反應和[3+2]-α-重氮酮環化反應 Catalytic [2+2]-Nitrosoarenes Cycloaddition and [3+2]-α-Aryl Diazoketones Annulation of 1,3-Dienes |
| 指導教授： |
劉瑞雄
Liu, Rai-Shung |
| 口試委員: |
彭之皓
Peng, Chi-How 吳明忠 Wu, Ming-Jung |
| 學位類別： |
碩士 Master |
| 系所名稱： |
理學院 - 化學系 Department of Chemistry |
| 論文出版年： | 2021 |
| 畢業學年度： | 109 |
| 語文別： | 中文 |
| 論文頁數： | 294 |
| 中文關鍵詞： | 四(3,5-二(三氟甲基)苯基)硼酸鈉 、亞硝基芳香烴 、[2+2]-環化加成 、4-胺基-1-環戊烯-3-酮 、哌啶 |
| 外文關鍵詞： | NaBARF, Nitrosoarenes, [2+2]-Cycloadditions, 4-Aminocyclopent-1-en-3-ones, Piperidones |
| 相關次數： | 點閱：2 下載：0 |
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第一章
此章展示了利用NaBARF催化2-酯基環戊二烯與亞硝基苯進行[2+2]-環化加成反應，得到兩個能夠分離之位置異構物的6-氧-7-雜氮二[3.2.0]庚環產物，且於熱平衡下重排為相同產物。由於此反應為可逆之[2+2]-亞硝基/烯環化加成反應，在熱反應平衡下，會具有選擇性的進一步生成4-胺基環戊烯-3-酮產物；在C(4)位置沒有取代基的情況下，受質則會在與亞硝基苯加成後，快速地進行擴環，有效率的得到一六環之哌啶酮產物。
第二章
此章節介紹了我們成功利用金金屬催化劑催化α-苯基重氮酮與三取代之烯類化合物進行[3+2]-環化反應，得到具有呋喃(furan)結構之產物。反應過程中，α-苯基重氮酮會形成α-氧代金碳烯中間體，此時烯類化合物能夠作為親核體攻打金碳烯中間體，形成一陽離子丙烯基中間體，最後環化得到有用的呋喃(furan)結構之產物。
Chapter I
NaBARF catalyzes the [2+2]-cycloaddition of 1,4-disubstituted cyclopenta-1,3-dien-2-yl esters with nitrsobenzene in toluene, affording two isolable regioisomers of 6-oxa-7-azabicyclo[3.2.0]heptanes, which thermally rearranged into the same 4-aminocyclopent-1-en-3-ones chemoselectively. The chemoselectivity of this reaction is due to a rapidly reversible nature of the initial [2+2]-nitroso/alkene cycloadditions. In the case of 4-substituted cyclopenta-1,3-dien-2-yl esters, their initial [2+2]-cycloaddition intermediates undergo a rapid ring expansion to afford six-membered piperidone derivatives efficiently.
Chapter II
Gold(I)-catalyzed [3+2]-annulations of α-aryl diazoketones with trisubstituted alkenes of substituted-1,3-butandienes affording the furan derivatives. In the mechanism, α-aryl diazoketones will turn into α-oxo gold carbenes. Afterwards, diene compounds as nucleophile attacks the gold carbene intermediates forming a allyl cation intermediates. Finally, the reaction proceeds cyclization and delivers the useful furan structure.
Chapter I
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Chapter II
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