臺灣博碩士論文加值系統

鈴木–宮浦偶合反應在合成聯苯化合物上是非常重要的方法之一，但現有的反應條件大多需使用對空氣與熱不穩定的含磷配位基。如何提高配位基的穩定性與減少催化劑的添加量進行反應是一項重要的課題。
本研究成功地利用商業上可購得之鄰苯二胺與吲哚-2-甲酸，合成一系列具有吲哚環和苯并咪唑環架構之新型碳氮配位基17、20。可在醋酸鈀添加量低 (0.5 mol%)、反應時間短 (1–2小時) 以及較溫和條件下 (60 ºC)，催化多樣性芳香溴化物進行鈴木–宮浦偶合反應，皆有良好之產率。較難進行的多取代雙芳香基化合物，可加入少許之添加劑，可達到92% 之產率。
為進一步挑戰更困難的不對稱鈴木偶合反應，引入掌性源並合成掌性配位基 28。而此研究的結果，則提供一個可以改進配位基特性的方向。
本研究所開發之配位基具空氣穩定性且合成流程簡易，適於工業應用並可大幅降低成本。

Suzuki-Miyaura coupling reaction has played an important role in the synthesis of biaryl compounds. Unfortunately, most of them require the use of air and/or thermally labile phosphine ligands. How to improve the ligand stability and to reduce the amount of catalyst needed has been one of the important synthetic issues.
This research has synthesized a series of novel C,N-ligands 17, 20 comprising indole and benzimidazole rings starting from commercially available phenyl diamine and indole 2-carboxylic acid. The Suzuki cross-coupling reaction of functionalized aryl bromides could be realized in the presence of low Pd-catalyst loading (0.5 mol%) under mild reaction conditions. These types of ligands are air/moisture stable and accessible with simple synthetic steps. For more difficult reactants such as tri-ortho-substituted biaryl compunds faster reaction rate (1-2 h) can be achieved in excellent yields at 60 C and the addition of additives.
Chiral C,N-ligands containing benzimidazolylindole backbone by introducing chiral source have also attempted. The highly challenging asymmetric Suzuki cross-coupling reaction employing these chiral C,N-ligands has been explored. The studies offer insights to improve the characteristics of chiral C,N-ligands.
In conclusion, our catalytic system can be applied to industrial manufacturing processes due to their high air/mosture stability and low cost.

目錄
摘要 i
Abstract ii
第一章 序論 1
1-1 前言 1
1-2 鈴木–宮浦偶合反應 3
1-3 鈴木–宮浦偶合反應之機制 4
1-3.1 氧化加成 5
1-3.2 金屬轉移 6
1-3.3 還原脫去 6
1-4 偶合反應催化劑發展 6
1-4.1 良好的偶合反應催化系統 6
1-4.1.1 商業上可購得之催化劑 7
1-4.1.2 自行研發之催化劑 7
1-4.1.2.1 磷基的催化活性 7
1-4.1.2.2 碳烯的催化活性 8
1-4.2 穩定的鈀環化合物 9
1-5 鈀環錯合物 9
1-5.1 鈀環錯合物之類型 9
1-5.2 鈀環錯合物應用於鈴木–宮浦偶合反應 10
1-6 不對稱催化鈴木–宮浦偶合反應 12
1-7 研究動機與方向 14
第二章 實驗結果與討論 17
2-1 以苯并咪唑與吲哚為架構之配位基 17–20 之合成 17
2-2 鈴木–宮浦偶合反應探討 20
2-2.1 搜尋最佳配位基與反應條件優選 20
2-2.2 碳氮配位基 17a 進行鈴木–宮浦偶合反應 26
2-3 不對稱鈴木-宮浦偶合反應探討 31
2-3.1 製備掌性配位基 28a–f 31
2-3.2 掌性碳氮配位基 28a–f 應用於不對稱鈴木–宮浦偶合
反應 32
2-4 結論 35
第三章：實驗步驟與數據 36
第四章：參考資料 70

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