臺灣博碩士論文加值系統

本研究將本位/鄰位帶有取代基之苯甲酸衍生物經由兩步驟的合成路徑合成出1-烷基-2-烯基芳香環化合物。首先，將苯甲酸經由Birch reduction在本位上引入烷基得到一1-烷基-2,5-環己二烯之非芳香性化合物衍生物。接著，利用鈀金屬催化進行碳-氫鍵活化/烯化後並回復芳香性。
烯基取代基會選擇性的引入苯環上鄰位的位置。藉由這個合成策略，我們可以使用容易取得的苯甲酸起始物，有效率並位置選擇性地合成1-烷基-2-烯基芳香環化合物。
關鍵字: 去芳香化、碳-氫鍵活化、再芳香化、烯化

A simple two-step ipso/ortho substitution of benzoic acid derivatives to afford 1-alkyl-2-olefinated arenes was developed. The alkyl substituents were first introduced into the ipso-position of benzoic acids via Birch reduction to give the dearomatized 1-alkyl-2,5-cyclohexadiene carboxylic acid derivatives. Next, the aromaticity can be regained by using a palladium-catalyzed directed C-H activation/olefination. The alkenyl substituents are regioselectively installed at the ortho-position. Using this protocol, we can efficiently and regioselectively synthesize 1-alkyl-2-olefinated arenes from commercially available benzoic acid derivatives.
Keywords: Dearomatization, C-H activation, rearomatization, olefination.

國家圖書館博碩士學位論文送存本延後公開申請書------------------------------------------I
論文電子檔案上網授權書 -------------------------------------------------------------------------II
學位論文審定書 ------------------------------------------------------------------------------------III
謝誌 --------------------------------------------------------------------------------------------------IV
目錄 ---------------------------------------------------------------------------------------------------V
表目錄 ---------------------------------------------------------------------------------------------VIII
圖目錄 -----------------------------------------------------------------------------------------------IX
中文摘要 ------------------------------------------------------------------------------------------XIII
英文摘要 ------------------------------------------------------------------------------------------XIV
第一章 前言 ------------------------------------------------------------------------------------------1
1.1導論 ------------------------------------------------------------------------------------------------1
第二章 文獻回顧 ------------------------------------------------------------------------------------3
2.1苯環上進行烷基化與烯基化反應 ------------------------------------------------------------3
第三章 結果與討論 -------------------------------------------------------------------------------16
3.1碳-氫鍵活化之探討 ----------------------------------------------------------------------------16
3.2反應最佳化條件表 -----------------------------------------------------------------------------17
3.2.1探討鈀催化劑對催化系統的影響 --------------------------------------------------------18
3.2.2探討氧化劑、溫度、溶劑對催化系統的影響 --------------------------------------------19
3.3合成不同羧酸起始物 --------------------------------------------------------------------------22
3.4由羧酸化合物合成(E)-3-(芳香基)丙烯酸酯 ----------------------------------------------23
3.5反應機構的鑑定 --------------------------------------------------------------------------------30
3.6以羧酸根為引導基團進行烯基化之探討 ------------------------------------------------33
3.7探討溫度、時間、催化劑、氧化劑對單取代烯基催化反應的影響-----------------34
3.8探討溶劑、氧氣對雙取代烯基化反應的影響 ---------------------------------------------36
3.9利用苯乙烯進行雙取代烯基化反應 -------------------------------------------------------38
3.10不對稱烯基化之探討 ------------------------------------------------------------------------42
第四章 結論 ----------------------------------------------------------------------------------------47
4.1實驗結論 -----------------------------------------------------------------------------------------47
4.2未來展望 -----------------------------------------------------------------------------------------52
第五章 實驗部分 ----------------------------------------------------------------------------------54
5.1 實驗儀器及部分細節 ------------------------------------------------------------------------54
5.2實驗一般步驟 (I) -------------------------------------------------------------------------------55
5.3利用Birch reduction製備起始物羧酸之實驗步驟 (II) ----------------------------------55
5.4.1氧化劑為Ag2CO3之鈀(II)催化耦合之實驗步驟 (III) ---------------------------------56
5.4.2氧化劑為BQ(1,4-Benzoquinone)之鈀(II)催化耦合之實驗步驟(IV)-----------------56
5.5.1保留羧基鈀(II)單邊烯化之催化耦合實驗步驟(V) -------------------------------------57
5.5.2保留羧基鈀(II)雙邊烯化之催化耦合實驗步驟(VI) ------------------------------------58
5.5.3保留羧基之鈀(II)催化耦合之不對稱雙邊烯化之實驗步驟(VII)-----------------58
5.5.4 脫羧氧化之鈀(II)催化耦合之不對稱雙邊烯化之實驗步驟(VIII) -----------------59
第六章 參考文獻 ----------------------------------------------------------------------------------59
附錄 ---------------------------------------------------------------------------------------------------63
一、光譜數據與物理性質 -------------------------------------------------------------------------63
二、X-ray單晶繞射資料 ---------------------------------------------------------------------------78
三、光譜附圖 ----------------------------------------------------------------------------------------89

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