本論文研究是藉由二價鈀金屬催化 9-(2-吡啶基)-9H-咔唑之鄰位碳－氫鍵活化/芳香化反應，利用芳香基三氟硼酸鉀鹽作為偶合試劑、硝酸銀為氧化劑、對位-苯醌為共同氧化劑及配位基，第三丁醇作為溶媒，並於 60-70 oC 下進行反應後，可以獲得一系列9-(2-吡啶基)-9H-咔唑之鄰位芳香基化產物 (45-98%)，且反應表現出高度的官能基耐受性。本反應關鍵的中間體， 9-(2-吡啶基)-9H-咔唑之鈀金屬錯合物可被製備單離，且透過X光單晶繞射分析進一步鑑定其結構。苯醌在此反應中扮演重要的氧化劑兼配位基角色，有效促進反應中之還原消去步驟的進行。動力學同位素效應之實驗結果為 0.87 (kH/kD)。 Hammett 實驗所獲得 ρ 值為 -2.14 (R2 = 0.90)。而吡啶導向基團可輕易被移除。最後基於所有的實驗數據，我們提出一個合理的反應機制。

A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation, in which palladium(II)-catalyzed cross-coupling of 9-(pyridin-2-yl)-9H-carbazoles with potassium aryltrifluoroborates is presented. Silver nitrate and tert-butanol were proved to be the best oxidant and solvent for the process, respectively. The product yields fluctuated from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, 9-(pyridin-2-yl)-9H-carbazole palladacycle was isolated and confirmed by X-ray crystallography. The kinetic isotope effect (kH/kD) for the C-H bond activation step was measured as 0.87. In addition, Hammett experiment gave a negative rho value, -2.14 with a reasonable correlation (R2 = 0.90). The directing group, pyridyl was demonstrated as a removable functional group. Finally, a rational catalytic mechanism is presented based on all experimental evidence.

誌謝 ……........................................................................................ i
中文摘要 ………………………………………………………………………… ii
英文摘要 ……………………………………………………………………… iii
第一章 過渡金屬催化碳－氫鍵活化 (C-H activation) 之介紹 ……...…… 1
第二章 主文 ……………………………………………………………………. 22
2-1 鈀金屬催化 9-(2-吡啶基)-9H-咔唑之鄰位碳-氫鍵活化/芳香基化研究 . 22
2-1-1 緒論 ……………………………………………………………………… 22
2-1-2 研究動機 ………………………………………………………………… 25
2-2 結果與討論 ……………………………………………………………… 26
2-2-1 前驅物 41a-d 之合成 ….……………………..………………………. 26
2-2-2 起始物 43a-j 之合成 …….................................................................... 26
2-2-3 9-(2-吡啶基)-9H-咔唑 (43a) 與苯基三氟硼酸鉀鹽 (36a) 於鈀
金屬催化碳－氫鍵活化/苯基化之反應條件最佳化 …………………. 30
2-2-4 9-(2-吡啶基)-9H-咔唑 (43a) 之鄰位碳－氫鍵活化/芳香基化反
應 ……………………………………………………………...……….... 33
2-2-5 9-(2-吡啶基)-9H-咔唑類似物 (43b-j) 之鄰位碳－氫鍵活化/苯基
化反應 …………………………………………………………………... 37
2-2-6 化合物 74d-g 與 75f-g 之結構位向鑑定 …………………………... 41
2-2-7 產物 72a-b 與 72k 之吡啶基團移除 ……………………………….. 52
2-2-8 Hyellazole (58a) 及其類似物 58d 之合成 ....................................... 52
2-2-9 化合物 74k 與 75k 之結構位向鑑定 ………………………………. 56
2-2-10 反應中間體的鑑定 …………………………………………………… 60
2-2-11 苯醌與氧化劑對反應之影響 ….................................................... 61
2-2-12 動力學同位素效應之研究 …………………………………………….. 61
2-2-13 Hammett 實驗 …………………………………….…………………… 66
2-2-14 反應機構的推測 ………………………………………………………. 67
2-2-15 利用環糊精於碳－氫鍵活化之位向控制研究 ................................... 69
2-3 結論 …………………………………………………………………….. 71
第三章 參考文獻與註釋 ………………………………………………………. 72
第四章 實驗部份 ………………………………………………………………. 79
4-1 儀器部分 …………………………………………………………………… 79
4-2 試藥部分 …………………………………………………………………… 80
4-3 實驗流程 …………………………………………………………………… 81
4-3-1 前驅物與起始物的製備流程 …………………………………………… 81
4-3-2 9-(2-吡啶基)-9H-咔唑 (43a) 之鄰位碳－氫鍵活化/芳香基化反應
的實驗步驟 …………………………………………………………….… 86
4-3-3 9-(2-吡啶基)-9H-咔唑類似物 (43b-j) 之鄰位碳－氫鍵活化/苯基
化反應的實驗步驟 …………………………..…………………………. 88
4-3-4 化合物 43k 之溴化與芳香基化反應之實驗步驟 .………………….... 89
4-3-5 產物吡啶基團移除之實驗步驟 ………………………………………. 90
4-3-6 palladacycle III 之合成步驟 ……………………………………………. 91
4-3-7 動力學同位素效應之實驗流程 ………………………………………… 91
4-3-8 Hammett 實驗之實驗流程 ……………………………………………... 92
4-3-9 環糊精於反應位向調控之實驗流程 …………………………………… 94
4-3-10 光譜數據與物理性質 …………………………………………………… 94
第五章 附錄 ……………………………………………………………………. 122
附錄 I 動力學同位素效應 …………………………………………………….. 122
附錄 II Hammett 方程式 ……………………………………………………… 127
附錄 III 化合物 72a 、 73a 、 palladacyle II 與 III 之晶體資料 ……… 130
第六章 光譜附圖 ………………………………………………………………. 192

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