銅(I)催化碳-氮偶合反應之研究

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姓名

陳世芳(Shih-Fang Chen) 查詢紙本館藏

畢業系所

化學學系

論文名稱

銅(I)催化碳-氮偶合反應之研究

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摘要(中)

以二苯胺類（HNPh2）/鹵化苯/碘化銅/1,10-二氮雜菲（Phen）/叔丁醇鹼（MOtBu, M=Li, Na, K）進行銅（I）催化碳-氮偶合反應系統已被研究多年，但是對於其銅（I）催化錯合物還是有所爭論，主要以[Phen-Cu-NPh2]與[Cu(NPh2)2]-為主。為了釐清此爭論，首先我們移去Phen這項變因，研究銅（I）如何進行催化。由DFT理論計算的結果指出，質子轉移（proton transfer, PT）平衡: MOtBu + HNPh2 ⇌ MNPh2 + HOtBu , GPT，影響了MNPh2在反應系統中的濃度，進而影響反應速率的快慢。因此我們直接使用MNPh2/鹵化苯/碘化銅進行實驗，以移去平衡所產生的干擾，其產率為LiNPh2 > NaNPh2 > KNPh2，這與我們所預測的催化物種M[Cu(NPh2)2]，其氧化加成反應活化能之結果相符合。另一方面，計算配位基置換（ligand exchange, LC）平衡: [Phen-Cu-NPh2] + MNPh2 ⇌ M[Cu(NPh2)2] + Phen , GLC，其結果GLC = -7.02 ~ -11.12 kcal/mol，表示Phen存在時，依然是以M[Cu(NPh2)2]為主要的存在物種。並且從MNPh2/鹵化苯/碘化銅/Phen催化實驗，Phen的加入反而會造成產率的下降，打破Phen會增加反應性的迷思。

摘要(英)

The C-N cross coupling catalyzed by NPh2H/ArI/CuI/1,10-Phenan- throline (phen)/MOtBu (M=Li, Na, K) system has been studied for many years. But the argument of Cu(I)-complex catalyst, which are [phen-Cu-NPh2] and M[Cu(NPh2)2], were still not stop. In order to clarify this argument, first we removed Phen to study Cu(I)-catalyzed mechanism. By density functional theory (DFT) studies, the proton transfer (PT) equilibrium, MOtBu + HNPh2 ⇌ MNPh2 + HOtBu, affects MNPh2 concentration, further the reaction rate is affected. Therefore, we directly used MNPh2/ArI/CuI system to remove the PT’s interferences, the result that the order of yield is LiNPh2 > NaNPh2 > KNPh2 corresponds with the oxidation-addition-activation-energy of M[Cu(NPh2)2], which were predicted our calculations. On the other hand, the calculated ligand exchange (LC) equilibrium, [Phen-Cu-NPh2] + MNPh2 ⇌ M[Cu(NPh2)2] + Phen, GLC, the results are GLC = -7.02 ~ -11.12 kcal/mol, which means that M[Cu(NPh2)2] is main species even if Phen is present. According to adding Phen accompanied decreasing yield in MNPh2/ArI/CuI/Phen experiments, this results breaking the myth of Phen enhanced reactivity.

關鍵字(中)

★ 碳-氮偶合反應
★ 銅一價催化
★ 銅一價
★ 1,10-二氮雜菲

關鍵字(英)

論文目次

摘要 IV
Abstract V
致謝 VI
目錄 VIII
圖目錄 XI
表目錄 XII
附錄 XIII
第一章緒論 1
1-1 前言 1
1-2 碳-氮鍵偶合反應之背景及簡介 3
1-2-1 起源：Ullmann-Goldberg偶合反應介紹 3
1-2-2 銅催化碳-氮偶合反應 4
1-2-3 銅催化碳-氮偶合反應一般反應機制 6
1-2-4 常見之碳-氮偶合反應系統 8
1-2-5 深入探討銅(I)催化碳-氮偶合反應機制 10
1-3 含碳雜環碳烯(NHC)背景及簡介 13
1-3-1 含氮雜環碳烯 (NHC) 金屬化 15
1-4 研究方向 16
第二章理論計算 18
2-1 HF理論方法 18
2-2 Density Functional Theory理論方法 19
2-3 基底 21
2-4 分裂（split）基底 22
2-5 極化函數（polarization function） 23
2-6 擴散函數（diffuse function） 24
2-7 限定自洽場與非限定自洽場 24
2-8 文獻回顧 26
第三章實驗 30
3-1 實驗藥品 30
3-1-1 溶劑 30
3-1-2 藥品 30
3-1-3 實驗氣體 31
3-2 實驗儀器 32
3-2-1 手套箱 (Dry box) 32
3-2-2 氣相層析儀 (GC) 32
3-2-3 氣相層析質譜儀(GC-MS) 32
3-2-4 核磁共振儀 (Nuclear magnetic resonance) 33
3-2-5 元素分析儀 (EA) 33
3-3實驗步驟-合成 34
3-3-1 合成IMes．HCl[31] 34
3-3-2 合成IPr．HCl[31] 35
3-3-3 合成IMes-Cu-Cl[31] 35
3-3-4 合成IPr-Cu-Cl[31] 36
3-3-5 合成1,3-Dimethylimidazolium iodide (簡稱：Met)[32] 36
3-3-6 合成LiNPh2[33] 36
3-3-7 合成NaNPh2[34] 37
3-3-8 合成KNPh2[35] 37
3-3-9 合成IMes-Cu-NPh2 38
3-4一般實驗步驟 39
3-4-1 1,10-二氮雜菲對銅催化碳-氮偶合之影響(叔丁醇鋰系統) 39
3-4-2 1,10-二氮雜菲對銅催化碳-氮偶合之影響(叔丁醇納系統) 41
3-4-3 1,10-二氮雜菲對銅催化碳-氮偶合之影響(叔丁醇鉀系統) 43
3-4-4 銅金屬含氮雜環碳烯錯合物對碳-氮偶合反應之影響 44
3-4-5 MNPh2之碳-氮偶合反應 48
3-5 理論計算實驗步驟 52
第四章結果與討論 53
4-1 1,10-二氮雜菲對銅催化碳-氮偶合之影響 53
4-2 銅(I)催化碳-氮偶合反應機制探討 57
4-3 MNPh2為起始物之銅(I)催化碳-氮偶合反應 63
4-4 配位基1,10-二氮雜菲與含氮雜環碳烯對於銅(I)催化碳-氮偶合反應之影響 67
4-5 含碳雜環碳烯配位基之討論 73
第五章結論 75
第六章參考文獻 76
第七章附錄 79

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指導教授

李光華、徐新光

審核日期

2014-7-25

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