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研究生： 何瑾璇
論文名稱： 1.矽陰離子與三羰鐵錯合物的加成反應 2.銠催化之分子內Pauson-Khand Reaction
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： 2003
畢業學年度： 91
語文別： 中文
論文頁數： 175
中文關鍵詞： 三羰鐵錯合物 、矽陰離子 、銠金屬 、分子內環化反應
英文關鍵詞： Davis reagent, silicon, rhodium, Pauson-Khand Reaction
論文種類： 學術論文
相關次數： 點閱：226  下載：0 
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    • 本論文共分成三部份：
    以三羰基鐵活化後的共軛雙烯，在不同溫度下，將碳的親核性試劑加成到（h4-1,3雙烯）三羰鐵錯合物後，所得的中間體與Davis reagent反應，可以得到一系列不同位置取代的雙烯鐵錯合物，其產物的種類與生成的反應中間體有絕對的關係。
    以有機矽陰離子為親核性試劑與雙烯三羰鐵錯合物進行加成反應，再以不同的親電子試劑終止反應，亦可得到一系列不同的有機矽化物。以Davis reagent終止時，產物保持原本雙烯三羰鐵的構造，然而以三氟醋酸或苯甲醯氯為親電子性試劑，則所得到的產物以乙烯基矽化物為主。從反應機構推測，閉環系統中矽陰離子會加成在電子密度較小的雙烯中間位置，而開環系統的矽陰離子則會加成到立障較小的雙烯末端。
    利用有機鋅銅試劑製備帶炔官能基之雙烯三羰鐵錯合物，再利用氧化劑將鐵去錯合，可得C-5位置帶炔官能基之環己雙烯化合物。以此為起始物，在銠金屬的催化下進行Pauson-Khand反應，結果可得到各式連結、架橋、螺旋多環化合物，並擁有好的立體選擇性和產率。

    The addition of reactive carbanions to (4-1,3-diene)Fe(CO)3 complexes at –78 ℃ and 25 ℃ produced putative homoallyl and allyl anion complexes, respectively. Reaction of the reactive intermediates with 2-(phenylsulfonyl)-3-phenyloxaziridine afforded nucleophilic substituted (4-1,3-diene)Fe(CO)3 complexes.
    The silicon anion (LiSiMe2Ph) is capable of addition to iron-complex. The addition affords silicon-substituted iron-complex after quenching with Davis reagent. The reaction path is similar to that of carbon nucleophiles. Quenching the reactive intermediate with trifluoroacetic acid or benzoyl chloride generated organosilicon compounds.
    The addition of alkyne-functionalized zinc-copper reagents to iron cation gives (4-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. Intramolecular cyclization of the alkynyl-substituted cyclohexa-1,3-dienes using 1 mol% of Rh(I) and carbon monoxide afforded fused, bridge or spiro cyclic compounds.

    目錄 i 中文摘要 iii 英文摘要 iv 第一章 緒論 1 第二章 以Davis Reagent終止雙烯三羰鐵錯合物之加成反應 2.1 前言 2.1.1（4-雙烯）三羰鐵錯合物之親核性加成反應 22 2.1.2 Davis reagent在有機合成的應用 30 2.2結果與討論 2.2.1三羰鐵陰離子錯合物在室溫下與Davis reagent的反應 38 2.2.2三羰鐵陰離子錯合物在-78℃下與Davis reagent的反應 47 2.3結論 49 第三章 矽陰離子與（4-雙烯）三羰鐵錯合物之加成反應 3.1前言 3.1.1有機矽化學的基礎反應類型 51 3.1.2矽陰離子在有機合成的應用 61 3.2結果與討論 3.2.1閉環（4-雙烯）三羰鐵錯合物與矽陰離子之加成反應 72 3.2.2.開環（4-雙烯）三羰鐵錯合物與矽陰離子之加成反應 80 3.3結論 84 第四章 銠催化之分子內Pauson-Khand Reaction 4.1前言 4.1.1由金屬催化之分子內環化反應 86 4.1.2 Pauson-Khand Reaction（PKR）的研究與演進 94 4.1.3以銠金屬催化之Pauson-Khand Reaction 104 4.2結果與討論 4.2.1 C-5位置帶炔官能基之1,3-環己雙烯的製備 106 4.2.2.以銠催化進行分子內Pauson-Khand Reaction 111 4.3結論 124 第五章 實驗部分 5.1分析儀器及基本實驗操作 125 5.2雙烯三羰鐵錯合物之加成反應 5.2.1一般實驗程序 127 5.2.2以Davis reagent終止雙烯三羰鐵之親核性加成反應 130 5.2.3雙烯三羰鐵錯合物與矽陰離子的加成反應 139 5.3銠催化之分子內Pauson-Khand Reaction 5.3.1一般實驗程序 147 5.3.2以銠金屬催化之PKR-type分子內環化反應 149 參考文獻 169 附圖 175

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