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| 研究生： |
陳柏強 Po-Chiang Chen |
|---|---|
| 論文名稱： |
過渡金屬催化二烯炔類化合物的環化反應 Transition-Metal Catalyzed Cyclization of Dienyne |
| 指導教授： |
劉瑞雄
Rai-Shung Liu |
| 口試委員: | |
| 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： | 2006 |
| 畢業學年度： | 94 |
| 語文別： | 中文 |
| 論文頁數： | 183 |
| 中文關鍵詞： | 金 、催化劑 、二烯炔 、環化反應 |
| 相關次數： | 點閱：2 下載：0 |
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摘 要
本論文主要是在針對二烯炔類化合物與金（Gold）催化劑反應的探討：首先會先就二烯炔類上官能基改變所造成的影響作探討；接下來將介紹利用串聯式（Tandem）的方法來改良反應。
首先觀察在二烯炔類化合物上置換不同的官能基（酯基、醇基、酮基、末端炔、非末端炔等等）的變化。
接著我們分別利用有機與金屬催化劑及金屬催化劑行串聯式（Tandem）的催化反應，使 3-en-1-yn-5-al 與環狀酮行醛-醇縮合反應（Aldol condensation），將反應的合成步驟大大的減少，而提高效率。
This work investigates the feasibility of catalytic cyclization of 6,6-disubstituted 3,5-dien-1-ynes via a 1,7-hydrogen shift. On the basis of this structure-activity relationship, we conclude that such a [1,7]-hydrogen shift is characterized by a “protonic” hydrogen shift, which should be catalyzed by π-alkyne activators. We prepared various 6,6-disubstituted 3,5-dien-1-ynes bearing various functional group, and found their thermal cyclizations to be greatly enhanced by AuCl3.
To achieve the atom economy, we have developed a tandem aldol condensation-dehydration and aromatization catalysis between cycloalkanones and special 3-en-1-yn-5-als using the weakly acidic catalyst CpRu(PPh3)2Cl and connected organocatalyst & AuCl3.
The deuterium-labelling experiments reveal two operable pathways for metal-catalyzed [1,7]-hydrogen shift of 3,5-dien-1-ynes. Either concerted [1,7]-hydrogen shift or proceeds through a proton dissociation and reprotonation process.
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