本論文共分三個部分，主要是利用過渡金屬催化或促進非環狀的烯炔類化合物進行環化反應。第一部份是以 Grubbs 教授所發展的釕金屬錯合物為催化劑，使對掌性二烯炔類化合物進行合環置換反應形成對掌性雙環醚類化合物，藉由乙烯氣體的通入，可減少氧原子對釕金屬產生螯合作用而降低其催化性，且利用取代基的不同，可選擇性的得到單一產物。而所得之雙環醚類結構是許多天然物的主要架構，故此催化反應可應用於天然物合成的研究上。
第二部份是利用鈷金屬錯合物促進順式環氧烯炔類化合物進行環化加成反應，形成三環內酯化合物。在此反應中，鈷金屬和環氧乙烷及炔基會先進行 [5+1] 的環化加成反應，形成六圓環的δ-內酯中間物，接著和烯基進行環化反應形成另外兩個環，並根據通入的氣體為二氧化碳或氮氣，形成含有環丁烷或環戊酮的三環內酯化合物。此種方法在合成複雜的多環分子上具有極高的應用價值。
第三部份是研究釕金屬錯合物 TpRu(PPh3)(CH3CN) 2PF6 催化烯二炔類進行芳香化反應，當炔基上接有長碳鏈時，碳-氫鍵會被活化而形成外接五圓環。而當我們以不同的親核性試劑如水、醇類、氨類等作為反應溶劑時，這些親核性試劑則會加成至芳香環上，並具有極高的位向選擇性，可應用於不同官能基芳香環衍生物的合成上。

Intramolecular cyclization of enynes mediated by organocobalt and ruthenium are discussed in this thesis. In the first chapter, we prepared a series of chiral 3,4-bisallyoxy-but-1-ynes having syn and anti configurations. Treatment of these substrates with Grubbs catalyst CL2(PCy3)2Ru=CHPh preferably gave chiral dioxabicyclo[4.4.0]- decane in addition to dioxabicyclo[5.3.0]decane in minor properties. On substitution of the 4-but-2-enyloxy group, the metathesis reactions produced only dioxabicyclo[5.3.0]decane in the presence of Grubbs ruthenium-imidazolidene carbine catalyst.
The second chapter discusses Co2(CO)8-mediated coupling of cis-epoxyalkyne, CO, and olefin functionalities, leading to tandem [5+1]/[2+2+1] and [5+1]/[2+2]-cycloaddition reactions to give tricyclic δ–lactones efficiently. The mechanism involves cyclocarbonylation to form δ–lactone intermediate, followed by oxidative cyclization to give cobalt-containing cyclopentane species. Insertion of CO or reductive elimination of this species leads to the derivative of cyclopentanone or cyclobutane products, respectively.
The third chapter describes TpRu(PPh3)(CH3CN) 2PF6 catalyzed aromatization of unfunctionalized endiynes. In the case of endiynes bearing a long alkyl substituent, the aromatization accompanied by a C-H bond insertion to form a cyclopentane ring. Highly nucleophilic addition of water, alcohols, aniline, acetylacetone, pyrroles and dimethyl malonate to endiynes gave functionalized benzene products in good yields. This method is very useful because it provides easy access to functionalized aromatic compounds from readily available unfunctionalized enediynes.

中文摘要 Ⅰ
英文摘要 Ⅲ
發表著作 Ⅴ
目錄 Ⅵ
圖目錄 .ⅩⅠ
表目錄 .ⅩⅥ
附圖目錄 .ⅩⅧ
實驗藥品之中英文對照 .ⅩⅩⅨ

第一章 釕金屬催化烯炔類形成雙環醚類化合物之環化反應

第一節 緒論 1
第二節 文獻回顧 2
2.1 前言 2
2.2 合環置換反應 3
第三節 結果與討論 5
3.1 實驗構思 5
3.2 配位基的合成 7
3.3 聯繼合環置換反應 12
3.3-1雙環醚類化合物的合成 12
3.3-2結構鑑定 13
3.3-3二烯炔類之合環置換反應 14
3.3-4選擇性合成雙環醚類化合物 16
3.4 反應機構的探討 17
第四節 結論 19
第五節 實驗部份 20
5.1 實驗的一般操作 20
5.2 化合物的合成 22
第六節 參考資料 53

第二章 鈷金屬促進順式環氧烯炔類形成三環內酯化合物之環化加成反應

第一節 緒論 57
第二節 文獻回顧 58
2.1 前言 58
2.2 Pauson-Khand 反應 58
2.3 利用不同金屬進行Pauson-Khand 反應 60
2.4 本實驗室之相關研究 62
第三節 結果與討論 64
3.1 實驗構思 64
3.2 配位基的合成 65
3.3 [5+1]/[2+2+1]和[5+1]/[2+2]環化加成反應 69
3.3-1 環化加成反應 69
3.3-2 結構鑑定 70
3.3-3 [5+1]/[2+2+1] 三環δ-內酯化合物的合成 72
3.3-4 [5+1]/[2+2] 三環δ-內酯化合物的合成 74
3.2 反應機構的探討 75
第四節 結論 77
第五節 實驗部份 78
5.1 實驗的一般操作 78
5.2 化合物的合成 80
第六節 參考資料 107

第三章 釕金屬催化烯二炔類進行親核性加成之芳香化反應

第一節 緒論 110
第二節 文獻回顧 111
2.1 前言 111
2.2 碳-氫鍵活化反應的發現 111
2.3 過渡金屬活化碳-氫鍵的相關反應 112
2.4 Bergman芳香化反應 115
第三節 結果與討論 120
3.1 實驗構思 120
3.2 配位基Tp與釕金屬的作用 121
3.3 催化劑[TpRu(CH3CN)2(PPh3)]PF6的製備 122
3.4 配位基的合成 123
3.5 活化碳-氫鍵之芳香化反應 126
3.5-1烯二炔類的芳香化反應 126
3.5-2實驗室同仁的研究成果 128
3.5-3同位素標定實驗 129
3.5-4反應機構的探討 130
3.6 親核性加成之芳香化反應 132
3.6-1氧原子之親核性加成 132
3.6-2碳原子之親核性加成 135
3.6-3氮原子之親核性加成 137
3.6-4以pyrrole作為親核性試劑 139
3.6-5實驗室同仁的相關研究 141
3.6-6同位素標定實驗 143
3.6-7反應機構的探討 144
3.7芳香化反應之後續研究 146
3.7-1配位基的合成 146
3.7-2碘化反應 147
3.7-3以鹵化物作為鹵素來源 148
第四節 結論 150
第五節 實驗部份 151
5.1 實驗的一般操作 151
5.2 化合物的合成 153
第六節 參考資料 202
附錄 210

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