中文摘要

最近幾年來由於氣候異常所造成的天災，讓人類開始注意自己所居住的地球環境維護，而迫使全世界去尋找對環境友善以及符合經濟效益的生產機制。在所有領域中，與生活息息相關的化學當然也沒缺席，因此，越來越多的團隊開始著手致力於綠色化學(green Chemistry)的研究與開發。在眾多反應中，過渡金屬催化反應具備條件溫和、低能源消耗、高度的位置(regio-)及立體位向(stereo-)選擇性、高官能基容忍度等優點，並且有效縮短化合物合成步驟，因而兼具環保與學術研究上之重要性，使得過渡金屬催化反應在近年來蓬勃發展。本篇論文分為四部份，分別探討有機金屬催化1-甲苯磺酰基腙-4-氧-5-炔、1,5-烯炔的環化加成反應與2-乙炔苯甲基醚的環化異構化反應。
第一部份利用銀金屬AgOTf催化1-甲苯磺酰基腙-4-氧-5-炔分子進行6-exo-dig含氮環化反應/[3+2]-環化加成序列反應。控制實驗發現

II
異喹啉與烯醚進行環化加成的活性極差，因此，我們推論極可能是非
芳香性兩性離子的中間體進行[3+2]偶極環化加成反應，並且排除異喹啉是中間體的可能性。
第二部份是發現1,5-烯炔在金金屬P(t-Bu)2(o-biphenyl)AuSbF6催化下與亞硝基苯進行環化/氧化性[3+2]-環化加成反應，形成三環的雜環產物。特別的是亞硝基苯在反應過程中除了作為兩個原子的建構單元外，也造成烯炔分子的氧化。此類反應在有機金屬催化烯炔環化加成反應中是史無前例的設計概念。

第三部份是延續第二部份的研究內容，以金金屬P(t-Bu)2(o-biphenyl)AuNTf2催化含環丙烷烯炔進行分子內環化反應生成環丙基金金屬亞甲基的中間體，接著，利用醛或亞硝基苯捕捉環丙
基金金屬亞甲基中間體，並經由擴環生成環丁烯衍生物。

III

第四部份是使用理想化金金屬催化劑與不同陰離子錯合物催化2-乙炔基芐基醚進行具位向選擇性的環化異構化反應而得到1-與3-取代2-甲氧基-1-氫-茚。BAr4F- 離子與分子塞存在下易生成1-取代的茚基醚，而NTf2- 與水存在下則易產生3-取代的茚基醚。此外，我們以臭氧將茚基醚進行氧化性斷鍵反應而有效地得到高度氧化的產物。

Chapter I
We report the Ag(I)-catalyzed tandem 6-exo-dig-azacyclization/[3+2] cycloaddition cascades on 1-tosylhydrazon-4-oxy-5-ynes to form complicated azacyclic products efficiently. Control experiments exclude the intermediacy of isoquinolinium species because of its poor activity in the cycloaddition with enol ether. We hypothesize that the [3+2] dipolar cycloadditions likely occur on non-aromatic zwitterionic intermediates.

Chapter II
We report herein the gold-catalyzed cyclization/oxidative [3+2] cycloadditions of 1,5-enynes with nitrosobenzenes. Notably, nitrosobenzenes not only provide two-atom building units, but also lead to the alkyne oxidation. Such a reaction pattern is unprecedented in metal-catalyzed cycloadditions of 1,n-enynes.
V

Chapter III
We have developed a formal [2+2+2] cycloaddition of 1,5-enyne with aldehydes or nitrosobenzenes to give cyclobutene derivatives. This reaction involves the cyclopropyl gold carbene intermediate, which is trapped by aldehydes or nitrosobenzenes.

Chapter IV
In this work, we demonstrate the effects of the counter anions (X) of P(t-Bu)2(o-biphenyl)X and water, to control the regioselective formation of 1- or 3-substituted 2-methoxy-1-H-indenes from the same

VI
2-alkynylbenzyl ethers; these two indenyl ethers can be oxidative cleaved by O3 to give two distinct highly oxygenated products, thus highlighting the synthetic utility.

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