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研究生: 游曼彤
Yu, Man-Tung
論文名稱: 鈷金屬錯合物催化碳-磷鍵偶合反應的研究
Cobalt-Catalyzed C-P Coupling Reactions
指導教授: 鄭建鴻
Cheng, Chien-Hong
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: 2010
畢業學年度: 99
語文別: 中文
論文頁數: 230
中文關鍵詞: 鈷金屬錯合物催化碳磷鍵偶合反應有機磷化合物三芳香環膦化合物膦氧化合物二苯基膦磷配位基芳香鹵化合物二苯基膦氧二芳基膦-噁唑啉配位基
外文關鍵詞: Cobalt-Catalyzed, carbon-phosphorus (C – P) bond, Coupling Reactions, organophosphines, unsymmetrical triarylphosphines, triarylphosphine oxides, diphenylphosphine, Arylphosphine ligands, aryl halides, diphenylphosphine oxide, phosphinooxazoline
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  • 有機磷化合物(organophosphines) 在勻相金屬催化反應(homogeneous catalysis) 中扮演相當重要的角色;然而,選擇合適的含磷配位基在催化反應中更是影響反應的結果關鍵。本篇論文探討以鈷金屬催化方式進行碳-磷鍵的偶合反應,使二苯基膦或二苯基膦氧與芳香鹵化物與鈷金屬進行加成反應,以合成出一系列具有高度合成應用價值的三芳香環膦化合物以及膦氧化合物,其加成方式與催化條件在相關領域中首次被報導。

    此外,本文進一步深入探討二苯基膦於此鈷金屬催化系統中可能之反應機構;有趣的是將Zn 替換為ZnI2,意即沒有還原劑將Co(II)I2還原成Co(I)I 時,反應仍然進行。而藉由實驗設計,將鋅試劑與二苯基膦進行反應測試,排除形成鋅試劑反應機構之可能性。

    本論文最後嘗試將所開發出來的鈷金屬催化碳-磷鍵偶合反應,應用於合成掌性二芳基膦-噁唑啉配位基 (PHOX),但所得到的結果是含有兩個掌性配位基的鈷金屬錯合物。


    Arylphosphine ligands play an extremely important role in homogeneous catalysis, and it’s also the crucial factor in determining the success of a reaction. In this thesis, we used an inexpensive cobalt-catalyzed to synthesize a species of unsymmetrical triarylphosphines and triarylphosphine oxides from diphenylphosphine or diphenylphosphine oxide with aryl halides. This is the first successful Co-catalyzed couplings of carbon-phosphorus (C – P) bond forming.

    In addition, we tried to study more details in the mechanism of the presenting coupling reaction. Interestingly, the reaction could also work without the reducing agent when the additive in the reaction condition was changed from Zn to ZnI2. Since the reaction failed to formation of carbon-phosphorus bond when replacing aryl halides by the organozinc reagent, the associative mechanism mediated by the organozinc reagent had been excluded.

    At the last part of this thesis, we attempted to synthesis of the phosphinooxazoline derivatves by this methodology. Finally, we got the corresponding complexes of two phosphinooxzaolines with cobalt iodides.

    中文摘要 I 英文摘要 II 謝誌 III 目錄 VII 名詞簡稱對照表 XI 表目錄 XII 圖目錄 XIV 鈷金屬錯合物催化碳-磷鍵偶合反應的研究 1、緒論 1 1.1、傳統有機合成方法 2 1.1.1 格林納試劑 (Grignard reagents) 的碳-磷鍵生成反應 2 1.1.2 鋰試劑 (Lithium reagents) 的碳-磷鍵生成反應 3 1.1.3 鋅試劑 (Zinc reagents) 的碳-磷鍵生成反應 3 1.2、過渡金屬催化碳-磷鍵偶合反應 4 1.2.1 鈀金屬錯合物催化碳-磷鍵的偶合反應 4 1.2.2 鎳金屬錯合物催化碳-磷鍵的偶合反應 8 1.2.3 銅金屬錯合物催化碳-磷鍵的偶合反應 10 1.3、其他特殊方法合成碳-磷鍵反應 13 1.3.1 微波方法 13 1.3.2 鹼金屬 13 1.4、鈷金屬應用於催化偶合反應 14 1.4.1 鈷金屬催化碳-碳鍵偶合反應 14 1.4.2 鈷金屬催化碳-氮鍵偶合反應 18 1.4.3 鈷金屬催化碳-硫鍵偶合反應 19 2、研究動機 20 3、實驗結果與討論 24 3.1、二苯基膦化合物與芳香鹵化物的碳-磷鍵偶合反應 24 3.1.1、二苯基膦化合物與芳香鹵化物的碳-磷鍵偶合反應 24 3.1.2、反應機構推測 39 3.1.3、結論 47 3.2、雙取代膦氧化合物與芳香鹵化物的碳-磷鍵偶合反應 48 3.2.1、二苯基膦氧化合物與芳香鹵化物的碳-磷鍵偶合反應 48 3.2.2、鈷催化雙取代膦氧化合物與碘甲苯進行偶合反應 57 3.2.3、反應機構推測 61 3.2.4、結論 62 4、碳-磷鍵偶合反應應用於合成掌性二芳基膦-噁唑啉配位基 (Phosphinooxazoline, PHOX) 63 4.1、研究動機 63 4.2、實驗結果與討論 65 4.3、結論 71 5、實驗部分 72 5.1 實驗儀器簡介 72 5.2 藥品資訊 73 5.3 實驗步驟與光譜數據 73 5.3.1 催化劑的製備 73 5.3.2 鈷催化碘化物與二苯基膦進行碳-磷鍵偶合之實驗通式 75 5.3.3 鈷催化碘化物與二苯基膦氧進行碳-磷鍵偶合之實驗通式 84 5.3.4 膦氧化合物起始物合成方法 91 5.3.5 鈷催化對碘甲苯與雙取代膦氧化合物進行碳-磷鍵偶合之實 驗通式 97 5.3.6 掌性鹵化物合成方法通式 100 6、參考文獻 104 附錄 1H, 13C NMR, 31P NMR 光譜圖 107 X-ray 光譜圖與數據 223

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