利用4-甲氧基-1,2-二烯-5-炔與苯並異噁唑進行金催化[4 + 1]環化反應如圖所示。環化機構中藉由形成氮烯、α-亞胺金碳烯和一、二號位連烯烴遷移形成(pyrrol-2-yl)methylgold 中間體。這些連烯烴取代的酯類基質，其金金屬中間體能進一步形成烯醇，進行羥醛反應，形成有用的pyrrolo[1,2-a]quinoline 衍生物。

Gold-catalyzed [4+1]-annulations of 4-methoxy-1,2-dienyl-5-ynes with benzisoxazole are described. The mechanism of these annulations involves nitrene formation of α-imino gold carbenes that undergo a 1,2-allene shift to form (pyrrol-2-yl)methylgold intermediates. With allenyl ester substrates, these gold intermediates become enolate species to enable intramolecular aldol reactions to form useful pyrrolo[1,2-a]quinoline derivatives.

中文摘要 ..................................................................... I
英文摘要 .................................................................... II
誌謝 ................................................................... III
期刊目錄 .................................................................... IV
英文縮寫對照表................................................................... V
第一節 緒論 ......................................................................1
1-1 金金屬催化劑及其反應軌域模型 ......................................................................1
1-2 pyrrolo[1,2-a]quinoline的生物活性 ......................................................................3
第二節 文獻回顧 ......................................................................4
2-1 藉由有機方法合成pyrrolo[1,2-a]quinoline ......................................................................4
2-2 藉由過渡金屬合成pyrrolo[1,2-a]quinoline ......................................................................5
2-3 連烯烴(Allene)的化學性質 ......................................................................6
2-3-1 以1-n-Allenyne為起始物進行金催化環化反應 ......................................................................6
2-3-2 利用5-連烯烴-1-炔類進行金催化自身環化 ......................................................................7
2-3-3 利用6-連烯烴-1-炔類進行金催化自身環化 ......................................................................8
2-3-4 利用7-連烯烴-1-炔類進行金催化水解自身環化 ......................................................................9
2-3-5 利用4-連烯烴-1-炔類進行金催化氧化環化反應 .................................................................... 10
2-3-6 利用6-連烯烴-1-炔類與苯基羥胺進行金催化環化反應 .................................................................... 11
2-4 苯並異噁唑(Benzisoxazole)的化學特性 .................................................................... 11
2-4-1 α-亞胺金碳烯(α-imino gold-carbene)的化學特性 .................................................................... 12
2-4-2 利用炔酰胺與苯並異噁唑進行金催化環化反應 ................................................................... 13
2-4-3 利用丙炔矽醚類與苯並異噁唑進行金催化環化反應 ................................................................... 13
2-4-4 利用丙炔酸酯類與苯並異噁唑進行金催化環化反應 .................................................................... 14
2-4-5 利用聯苯乙炔與苯並異噁唑進行金催化環化反應 ................................................................... 15
2-4-6 利用3-連烯烴-1-烯類與苯並異噁唑進行金催化環化反應 .................................................................... 16
2-4-7 利用N-芳香基炔酰胺與苯並異噁唑進行金催化環化反應 ................................................................... 17
2-4-8 利用N-苯甲基炔酰胺與苯並異噁唑進行金催化環化反應 ................................................................... 18
2-4-9 利用aryloxyethyne與苯並異噁唑進行金催化環化反應.................................................................. 20
第三節 結果與討論 .................................................................... 20
3-1 實驗動機與構思 .................................................................... 20
3-2 最佳化反應條件 .................................................................... 21
3-3 金催化多種連烯烴分子與苯並異噁唑進行環化反應的範圍 .................................................................... 23
3-4 金催化連烯烴分子與多種苯並異噁唑進行環化反應的範圍 ................................................................... 24
3-5 金催化連烯烴分子與多種異噁唑進行環化反應的範圍 .................................................................... 25
3-6 對照實驗之探討 .................................................................... 27
3-7 反應機構探討 .................................................................... 28
第四節 結論 .................................................................... 28
第五節 實驗部分 .................................................................... 29
5-1 實驗之一般操作 .................................................................... 29
5-2 實驗基質之合成 .................................................................... 30
1. 基質1a之合成方法 .................................................................... 30
2. 基質2a之合成方法 .................................................................... 31
3. 基質4a之合成方法 .................................................................... 32
4. 基質6a之合成方法 .................................................................... 33
5. 基質6h之合成方法 .................................................................... 34
6. 基質6i之合成方法 .................................................................... 35
5-3 催化反應之操作 .................................................................... 36
1. 3a合成實驗操作步驟 .................................................................... 36
2. 5a合成實驗操作步驟 .................................................................... 36
5-4 實驗光譜數據資料 .................................................................... 37
5-5 X-射線結晶結構和數據(3a, 3a’, 5a, 7c) .................................................................... 56
第六節 參考資料 .................................................................... 92

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