研究生: |
戴志娟 |
---|---|
論文名稱: |
銠金屬之環戊烯酮合成研究 |
指導教授: |
葉名倉
Yeh, Ming-Chang |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2004 |
畢業學年度: | 92 |
語文別: | 中文 |
論文頁數: | 117 |
中文關鍵詞: | Pauson-Khand Reaction 、銠金屬 |
英文關鍵詞: | Pauson-Khand Reaction, Rhodium |
論文種類: | 學術論文 |
相關次數: | 點閱:152 下載:5 |
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利用有機鋅銅試劑製備帶炔官能基之雙烯三鐵錯合物,再加入氧化劑(CAN)將鐵去錯合,可得C5位置帶炔之環己雙烯化合物。再以C5位置帶炔之環己雙烯化合物為起始物,在銠金屬的催化下進行Pauson-Khand 反應(PKR)。
上述起始物以數個串聯的亞甲基為側鏈,連接炔基和環戊雙烯。當起始物的側鏈為兩個亞甲基時,進行PKR可以得到預期的合環產物;而起始物的側鏈改為三個亞甲基時,進行PKR可以得到預期的合環產物,以及三環連結產物,這個意外的發現來自於起始物進行雙烯轉移後的PKR產物。
The addition of alkyne-functionalized zinc-copper reagents to iron cation gives (η4-cyclohexa-1,3-diene)Fe(CO)3 complexes with an alkyne-functionalized side-chain at C-5 position of the ring. Decomplexation of the complexes with diammonium cerium(IV) nitrate afforded cyclohexadienyne compound. The alkynyl-substituted cyclohexa-1,3-dienes underwent intramolecular cyclization using 1 mol% of Rh(I) and carbon monoxide.
The rhodium-catalyzed Pauson-Khand reaction (PKR) of cyclohexa-1,3-dienes containing two methylene carbons and an alkyne in a chain produced regular PKR products. Cyclohexadienynes bearing three methylene units and a aromatic ring at the alkyne afforded regular PKR products and angularly fused tricyclic compounds, which were derived from diene migration followed by the PKR process.
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