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研究生:梁中昊
研究生(外文):Chung-hao Liang
論文名稱:以鎳金屬催化帶官能基1,3-環己二烯分子內環化反應之研究
論文名稱(外文):Nickel-Mediated Intramolecular Cyclization of 1,3-Dienes Containing Various Functional Groups
指導教授:葉名倉
指導教授(外文):Ming-Chang P. Yeh
學位類別:碩士
校院名稱:國立臺灣師範大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:209
中文關鍵詞:分子內環化反應13-環己二烯連結雙環化合物
外文關鍵詞:nickelintramolecular cyclization13-cyclohexadienefused bicyclic compound
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利用(η5-1,3-環己雙烯)三羰鐵錯鹽與帶官能基鋅銅試劑反應,合成一系列C-5位置上帶官能基1,3-環己雙烯三羰鐵衍生物。經過Ce(IV)氧化去錯合後,可得到帶官能基共軛環己雙烯衍生物。
當C-5碳鏈長度為一,醛為官能基時,可得到橋頭雙環[3.2.1]化合物;當碳鏈長度為二,三時,可順利形成聯結雙環化合物。當碳鏈長度為四時,則會形成螺旋雙環化合物,若碳鏈長度為五時,則因為位置太遠,無法形成好的過渡狀態,因此無法進行合環反應。以酮基為官能基時,由於酮基本身活性較小,立障較大,所以產率均不佳,且環化產物無規則性。
以芳香醛為官能基時,只有在鄰位(ortho)取代會發生環化反應,反應溫度的高低可控制產物的比例:當反應溫度較低(35℃)時,偏向金屬與不飽和鍵之加成反應;當溫度較高時(55℃),以H-Ni-SiEt3加成至雙烯反應機構進行者增加,但是仍以金屬與不飽和鍵之加成反應為主。
將側鏈放置雜原子,形成帶有雜原子雙烯化合物時,由於無法成功進行去錯合反應,因此無法將我們研究範圍擴大。
本論文將探討以帶官能基1,3-環己雙烯衍生物利用鎳金屬催化分子內環化反應的限制及應用,並對未來發展做一展望。

Ni(cod)2 is a powerful catalyst for intramolecular cyclization of 1,3-cyclohexadienes bearing a tethered aldehyde. The starting diene-aldehyde compounds are easily available using our own developed methods.
Treatment of the catalytic amount of Ni(cod)2, PPh3, and HSiEt3 (5 molar equiv) with cyclohexad-1,3-dienes containing a tethered aldehyde produced fused-, spiro- or bridged-bicyclic skeleton depending on the length of the side-chain( -(CH2)nCHO). With one carbon (n= 1), bridged-bicyclic compounds were isolated; with two or three carbons (n= 2 or 3), fused-bicyclic skleton were the major cyclized products, with four carbons (n= 4), spiro-bicyclic compounds were generated, with five carbons on the side-chain (n= 5), the intramolecular cyclization failed, the reduction of the aldehyde occurred to give dienol derivatives.
Cyclohexa-1,3-dienes containing an ortho aromatic aldehyde also underwent intramolecular cyclization under the similar reaction conditions. Tricyclic skeletons were isolated in good yields.
The scope and limitations of the nickel-mediated intramolecular cyclization of 1, 3-cyclohexadienes containing various functional groups will also be discussed.

目錄 i
中文摘要 iii
英文摘要 iv
第一章 緒論 1
第二章 鎳金屬催化帶官能基 1,3-環己二烯衍生物分子內環化反應之研究
2.1 前言 18
2.2 開環1,3-雙烯醛 (5Z)-5,7-Octadienal II-113 分子內環化反應之研究 35
2.3 1,3-環己二烯醛衍生物分子內環化反應之研究 40
2.4共軛雙烯酮衍生物之製備與分子內環化反應之研究 53
2.5共軛雙烯芳香醛衍生物之製備與分子內環化反應之研究 58
2.6 含雜原子側鏈共軛雙烯醛衍生物之製備與分子內環化反應之研究 66
2.7 鎳金屬催化氫氰化反應(hydrocyanation)之研究 69
2.8 結論 71
第三章 實驗部分
3.1分析儀器及基本實驗操作 72
3.2 帶官能基有機鋅銅試劑的制備 73
3.3 一般實驗程序 74
3.4.1 開環共軛雙烯酯II-122與開環共軛雙烯醛II-113的製備 77
3.4.2 環化產物II-124 之合成 77
3.5.1 帶官能基1,3-環己雙烯衍生物與1,3-環己雙烯醛衍生物之製備 78
3.5.2 1,3-環己雙烯醛之分子內環化反應 84
3.6.1 1,3-環己二烯酮衍生物的製備 86
3.6.2 1,3-環己二烯酮分子內環化反應 87
3.7.1 1,3-環己雙烯芳香酮衍生物之製備 89
3.7.2 1,3-環己雙烯芳香醛衍生物分子內環化反應 91
3.7.3 含三乙基矽烷保護基之去保護反應 92
3.8 帶氧原子側鏈衍生物的製備 94
3.8.2 帶氧原子側鏈1,3-環己雙烯醛衍生物的製備 96
3.9 4-Cyclohexa-2,4-dienyl-2-hydroxy-butyronitrile 209的合成 97
第四章 參考文獻 99

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