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研究生： 劉佳茹
Liu, Chia-ju
論文名稱： 鈀錯合物催化烯類之耦合反應: 合成(E)-1,2-二芳香基乙烯
Palladium-Catalyzed Coupling of Alkenes: Synthesis of (E)-Stilbenes
指導教授： 吳耀庭
Wu, Yao-Ting
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： 2009
畢業學年度： 97
語文別： 中文
論文頁數： 102
中文關鍵詞： 烯烴耦合反應 、金屬鈀催化
外文關鍵詞： Palladium Catalyzed
相關次數： 點閱：51  下載：3 
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    • 4-甲基苯乙烯 (1a) 於鈀錯合物催化下可和苯基硼酸 (3a) 進行耦合反應，合成(E)-1-苯基-2-(4-甲基苯基)-乙烯 (E-4ba)。利用此合成方法，已製備23種三聚合衍生物，此方法提供很高的位向選擇性及不錯的產率。
    在測試反應中發現鈀金屬催化劑、氧化劑、無機鹼均扮演關鍵的角色。反應條件已調整至最佳化：將4-甲基苯乙烯 (4b)、苯基硼酸 (3a)、醋酸鈀(II)、醋酸銀及二水合磷酸氫二鈉，溶於1,2-二氯乙烷溶劑，在40-45 ºC下，經過約24小時，可得到產率96 %的 (E)-1-苯基-2-(4-甲基苯基)-乙烯 (E-4ba)。在此反應條件下，多種官能基硼酸化合物皆可進行偶合反應，具有高度的官能基容忍度，更發現2-噻吩硼酸 (3u) 可和4-甲基苯乙烯 (4b) 進行兩次耦合反應生成 (E,E)-2,5-雙(2-(4-甲基苯基)乙烯基)噻吩，產率60 %。若只加入烯烴化合物或硼酸化合物也可進行自身耦合反應，分別生成 (1E,3E)-丁二烯化合物 (2) 和聯苯化合物 (7)。根據實驗結果，產物 (E)-1,2-雙取代乙烯化合物4可能經由兩種反應路徑而形成，主要途徑是經由類似Heck Reaction的反應機構，鈀金屬催化劑與硼酸化合物形成芳香鈀錯合物，再與烯烴化合物配位合成化合物4，另一途徑則活化烯烴化合物的CH鍵再與硼酸化合物進行耦合反應。

    Various 1,2-disubstituented ethenes 4 have been generated by the Pd-catalyzed cross-coupling of alkenes 1 and boronic acids 3. Based on this synthetic method, twenty-three ethene derivatives have been prepared in 22-97% yields. This procedure provides high regioselectivity to generate adducts E-4 in moderate to excellent yields.
    Systematic studies of the reaction conditions revealed that palladium catalyst, oxidant and base all play key roles. The reaction conditions have been optimized. Upon heating 4-methylstyrene (1b) and phenylboronic acid (3a) in 1,2-dichloroetheane at 40-45 ºC with a mixture of Pd(OAc)2, AgOAc and Na2HPO4.2H2O, (E)-4-methylstilbene (E-4ba) can be obtained with high regioselectivity in 96 % yield. Coupling of 2-thienylboronic acid (2u) with 4-methylstyrene (1b) furnished (E,E)-2,5-bis[2-(4-totyl)ethenyl]thiophene (60 %). Our reaction conditions tolerated a wide range of functional groups. Moreover, in the absence of boronic acids 3, alkenes 1 undergo dimerization to yield 1,3-butadienes 2. On the other hand, in the absence of alkenes 1, boronic acids 3 undergo dimerization to yield biphenyls 7. This control experiment indicates that the formation of 4 should via: 1) palladium catalyst through transmetallation with boronic acid to form aryl palladium intermediate and 2) the alkenyl CH bond activation.

    目錄 中文摘要.......................................................................................................III 英文摘要.......................................................................................................IV 誌謝................................................................................................................VI 表目錄...........................................................................................................IX 圖目錄............................................................................................................X 壹、 前言.........................................................................................................1 貳、 結果與討論.........................................................................................14 一、 由芳香烯烴化合物合成(1E,3E)-1,4-二芳香基-1,3-丁二烯化合物….14 (一) 二聚合反應催化系統之探討................................................................14 1. 探討鈀催化劑對二聚合反應的影響........................................................15 2. 探討氧化劑、溫度、反應時間對二聚合反應的影響................................16 3. 探討溶劑對二聚合反應的影響................................................................18 4. 探討無機鹼對二聚合反應的影響............................................................20 二、 由芳香烯烴化合物合成(E)-1,2-二芳香基乙烯化合物....................... 22 (一) 合成(E)-1,2-二取代基乙烯之方法........................................................22 (二) 與芳香基硼酸化合物耦合反應系統之探討........................................25 1. 探討烯烴化合物與芳香基硼酸化合物比例和反應時間對耦合反應的影響.....................................................................................................................26 2. 探討氧化劑對耦合反應的影響................................................................27 3. 探討鈀催化劑對耦合反應的影響............................................................28 4. 探討無機鹼對耦合反應的影響................................................................29 5. 探討反應溫度對耦合反應的影響............................................................31 (三) 由烯烴化合物合成(E)-1,2-二芳香基乙烯化合物................................33 1. 探討烯烴化合物上取代基對耦合反應的影響........................................34 2. 探討芳香基硼酸化合物上取代基對耦合反應的影響............................37 3. 合成1,1,2-三苯基乙烯...........................................................................41 4. 合成1,3-丁二烯化合物和聯苯化合物.....................................................42 (四) 推測之反應機構....................................................................................44 參、 結論.......................................................................................................46 肆、 實驗.......................................................................................................48 伍、 參考文獻..............................................................................................70 陸、 附錄.......................................................................................................75 一、 核磁共振光譜圖.....................................................................................75   表目錄 表一、 鈀催化劑對二聚合反應的影響.........................................................15 表二、 氧化劑、溫度、反應時間對二聚合反應的影響.................................17 表三、 溶劑對二聚合反應的影響.................................................................19 表四、 無機鹼對二聚合反應的影響.............................................................21 表五、 4-甲基苯乙烯與苯基硼酸劑量比例和反應時間對耦合反應的影響.....................................................................................................................27 表六、 氧化劑對耦合反應的影響.................................................................28 表七、 鈀催化劑對耦合反應的影響.............................................................29 表八、 無機鹼對耦合反應的影響.................................................................30 表九、 反應溫度對耦合反應的影響.............................................................31 表十、 烯烴化合物上取代基對耦合反應的影響.........................................36 表十一、 硼酸化合物上取代基對耦合反應的影響.....................................39 表十二、 合成1,3-丁二烯化合物2和聯苯化合物7.....................................43   圖目錄 圖一、 經由鈀催化烯烴化合物和芳香烴衍生物之耦合反應.......................2 圖二、 鈀催化苯乙烯和碘化苯之交叉耦合反應...........................................3 圖三、 鈀催化烯烴化合物之Heck Reaction...................................................4 圖四、 Heck Reaction反應機制......................................................................4 圖五、 鎳催化苯基溴化鎂和鹵化烯烴之交叉耦合反應...............................5 圖六、 鎳/鈀催化烯烴化合物之Kumada Coupling.......................................6 圖七、 Kumada Coupling反應機制.................................................................6 圖八、 鈀催化烯烴鹵化物和炔烴氯化鋅之交叉耦合反應...........................7 圖九、 鎳/鈀催化Negishi Coupling交叉耦合反應.........................................8 圖十、 鈀催化Stille Coupling之交叉耦合反應..............................................8 圖十一、 四(三苯基磷)化鈀催化苯基硼酸進行交叉耦合反應....................9 圖十二、 鈀/鎳催化Suzuki Coupling之交叉耦合反應..................................9 圖十三、 Suzuki Coupling的反應機制..........................................................10 圖十四、 鈀催化芳香烴和烯烴之耦合反應………………….....................11 圖十五、 鈀催化芳香烴酸之脫羧耦合反應.................................................12 圖十六、 鈀錯合物催化4-甲基苯乙烯二聚合反應之發現.........................13 圖十七、 鈀催化烯烴化合物與芳香基硼酸化合物之耦合反應.................13 圖十八、 測試二聚合反應之最適化條件.....................................................14 圖十九、 合成(E)-1,2-二取代基乙烯4方法.................................................24 圖二十、 (E)-1-苯基-2-(4-甲基苯基)乙烯4ba的合成.................................25 圖二十一、 1,1,2-三苯基乙烯的合成............................................................41 圖二十二、 推測的反應機制.........................................................................45

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