銅催化碳硫偶合反應之陽離子效應研究

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姓名

張原銘(Yuan-ming Chang) 查詢紙本館藏

畢業系所

化學學系

論文名稱

銅催化碳硫偶合反應之陽離子效應研究
(The cation effect of copper catalyzed C-S coupling study)

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摘要(中)

以銅(I)催化劑進行偶合反應生成碳-硫鍵，一直以來被廣泛應用於有機合成、天然物藥物合成。通常是在含有鹵化銅、配位基和鹼類的反應。在這篇論文中，我們發現在此催化系統中之反應性受到不同鹼金族陽離子以及配位基的影響。因此，我們猜測其反應途徑可能會先形成[Cu(SPh)2]一和 Cu(SPh)的平衡，再進行氧化加成作用。
目前尚未直接的分離或直接觀察出催化系統下的中間產物。因此我們藉由in situ ESI-MS高溫下觀測到[Cu(SPh)2]一、配位基抓住鹼金族陽離子等的訊號，進而推測其反應性是受到鹼(鹼金族陽離子)的影響。而s K-edge X- ray 吸收光譜也可以定性地解釋不同的鹼(鹼金族陽離子)如何影響碳硫偶合的反應性，並說明配位基在催化系統中所扮演的角色。

摘要(英)

The reactions of copper(Ⅰ)-catalyzed cross-coupling C-S bond formation have been widely used in organic synthesis, the synthesis of natural products and pharmaceuticals. The common methods for the C-S coupling require copper, base, and ligands. In this thesis, the reaction of thiophenol and iodobenzene forms diaryl sulfides were affected by metal cation and ligands.Therefore, we proposed the equilibrium between [Cu(SPh)2]一 and Cu(SPh) before going to oxidative additive reaction.
However, the direct isolation or observation of intermediates can not be achieved. Thus, we used in situ ESI-MS to find out the intermediates of catalytic reaction. We observed [Cu(SPh)2]一 and alkali metal cations trapped by ligands in reaction solutions. Moreover, the sulfur K-edge X-ray absorption spectrum could qualitatively explain how the different bases(cations) affect the catalytic system and why ligands could enhance the reactivity of this catalytic system.

關鍵字(中)

★ 碳硫偶合反應
★ 銅催化

關鍵字(英)

★ Copper catalyzed
★ C-S coupling

論文目次

摘要 ........................................................................................ I
目錄 .......................................................................................................... IV
表目錄 ...................................................................................................... IX
第一章、緒論............................................................................................. 1
1-1 碳-硫鍵偶合反應之背景及簡介 ................................................. 1
1-2.電灑式游離化質譜(Electrospray Ionization Mass Spectroscopy) ............................................................................................................ 19
1-3.同步輻射中心BL16A及EXANES介紹 ................................. 24
第二章、實驗部分 .................................................................................. 30
2-1 實驗藥品 .................................................................................... 30
2-1.1 溶劑 .................................................................................. 30
2-1.2藥品 ................................................................................... 30
2-1.3氣體 ................................................................................... 31
2-2實驗儀器 ..................................................................................... 32
2-2.1 手套箱(Dry box) .............................................................. 32
2-2.2液相層析電灑游離化質譜儀 ........................................... 32
2-3實驗步驟 ..................................................................................... 33
2-3.1 CuI / MOtBu 催化進行碳-硫鍵偶合反應 ....................... 33
2-3.2直接於催化反應條件進行下進行電灑式游離法質譜分析
V
..................................................................................................... 33
2-3.3 Cu(Ι)-催化進行碳-硫鍵偶合反應(起始物為苯硫酚) ..... 33
2-3.4 加入冠醚探討其對反應性的影響 .................................. 34
2-3.5加入冠醚的樣品進行電灑式游離法質譜分析 ............... 34
2-3.6氣相層析儀實驗 ............................................................... 34
2-3.7 準確質譜分析實驗 .......................................................... 35
2-3.8 氣相層析儀實驗 .............................................................. 36
第三章、結果與討論 .............................................................................. 37
3-1以改變起始物(鄰-甲苯硫酚與苯硫酚)比較Cu(I)催化劑催化反應 ........................................................................................................ 37
3-2 in situ ESI-MS 在銅(Ⅰ)催化下實驗測試 ................................ 39
3-4.同步輻射中心樣品吸收光譜討論 ............................................. 46
3-4.1.分子軌域計算(MO計算) ................................................. 46
3-4.2 理論計算之吸收光譜討論 .............................................. 46
3-4.3實驗之吸收光譜討論 ....................................................... 50
第四章、結論........................................................................................... 57
附錄 ........................................................................................................... 58
參考文獻 ................................................................................................... 71

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指導教授

許益瑞、李光華、徐新光
(I-Jui Hsu、Kwang-Hwa Lii、Shin-Guang Shyu)

審核日期

2012-7-12

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