有機金屬鋅催化炔醯胺類與Chloramine-T進行氯胺化反應和有機金屬金催化兩分子炔醯胺類與烯類進行立體選擇性[2+2+2]環加成反應

Zinc-Catalyzed Chloroamination reaction of Ynamides and Chloramine-T And Gold-Catalyzed Regiocontrolled [2+2+2]-Cycloadditions of Two Terminal Ynamides with Vinyl ether

陳佳杏(Chen, Chia Hsing)

指導教授 ： 劉瑞雄

國立清華大學/理學院/化學系/碩士(2016年)

摘要

第一章

經由有效的鋅催化劑，將中端炔和Chloramine-T在室溫下進行氯胺化，在溫和的條件下，得到高產率的雙氯亞胺形式的產物（(Z)-2,2-dichloro-N-methyl-N-(methylsulfonyl)-2-phenyl-N'-tosylacetimidamide），產物還具備的兩個缺電子基團，容易與其他不同的親核試劑進行下一步反應。

第二章

利用金金屬催化劑，催化兩個末端炔醯胺和烯類進行立體選擇性[2+2+2]-環加成反應，建構出多取代苯環的衍生物，這種新的環加成反應的效用適用在廣泛範圍的炔醯胺和乙烯基乙醚或2-甲氧基丙烯有優異的區域選擇性與表現，且目前較少例子是使用烯烴，來進行[2+2+2]合環反應。

關鍵字

鋅金屬催化 ； 氯胺化反應 ； 金金屬催化 ； [2+2+2]合環

並列摘要

PART 1

The synthesis of (Z)-2,2-dichloro-N-methyl-N-(methyl-sulfonyl) -2-phenyl-N'-tosylacetimidamide, an efficient zinc catalyzed reaction enhancing the reactivity for the chloroamination of alkynes with Chloramine-T at room temperature, is described with moderate to good yields. The electron-deficient character of the azomethine group of polyhalogenaldimines promotes their interactions with numerous nucleophiles, which could be used for further reactions.

PART 2

This part of the dissertation deals with the gold-catalyzed regiocontrolled [2+2+2]cycloadditions of two ynamides and vinyl ether constructing polysubstituted benzene derivatives. The utility of this new cycloaddition is manifested in the excellent regioselectivity with a wide range of scope of applicable ynamides as well as vinyl ether. And there are few examples using alkene for [2+2+2]cyclization reactions.

並列關鍵字

Zinc catalyst ； Gold catalyst ； chloroamination ； cycloadditions

參考文獻

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