碘化鋅誘導之ω-矽炔-α-氰基環酮分子內環化反應—迅速建構烯環戊烷與烯環己烷的新合成方法

Zinc Iodide Mediated Cyclization of ω-Silylalkynyl-α-cyanoketones—A Facile Methylenecyclopentane and Methylenecyclohexane Annulation Process

廖正峰(Cheng-Feng Liao)

指導教授 ： 劉行讓

國立清華大學/理學院/化學系/碩士(2006年)

摘要

本論文主要探討碘化鋅誘導之omega-矽炔-alpha-氰基環酮分子內環化反應。我們使用一系列的alpha-氰基環烯酮進行1,4-加成反應引入具有三甲基矽丁炔的側鍵，再將此一系列的omega-矽炔-alpha-氰酮化合物 2 經碘化鋅作用下，可進行分子內環化反應，得到建構出烯環戊烷產物3。除此之外，只要使用多延伸一個碳的Grignard試劑，即可得到化合物4，再經由相同的反應條件可獲得建構出烯環己烷產物5。此反應有著高產率、高立體及幾何選擇性之優點。這個新發展的合成方法預期可有效地應用於複雜有機化合物的合成。

關鍵字

碘化鋅 ； 烯環戊烷 ； 烯環己烷 ； 1,4-加成 ； 氰基環酮

並列摘要

Construction of a methylenecyclopentane ring is an important issue in synthesis of natural products. This thesis delineated a newly developed process toward highly functionalized methylenecyclopentanes. Recently, we developed an efficient methylenecyclopentane annulation process to construct the functionalized methylenecyclopentanes. The efficient methylenecyclopentane annulation involves a convenient 1,4-addition of (4-buty-1-nyl)trimethylsilane magnesium chloride to 2-cyano-2-cycloalkenone 1 and following a zinc iodide promoted annulation of the resulting bicyclic product 3. We also developed the process toward methylenecyclohexane annulation via compound 4 under the same condition. This annulation process can be accomplished in mild condition and the yield is high. The utility of the functionalized methylenecyclopentane annulation was also be studied.

並列關鍵字

Zinc iodide ； methylenecyclopentane ； methylenecyclohexane ； 1,4-addition ； alpha-cyanoketone

參考文獻

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