利用有機膦試劑作為催化劑對 2-Arylidine-1,3-Indandione 進行 β-位醯化反應和以分子內 Wittig 反應進行吲哚與呋喃之化學選擇性合成

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2013

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本論文可分成兩大主題,在第一部分中使用催化量的有機膦試劑對 2-Arylidine-1,3-indandione 做直接 β-位之醯化反應;並在第二部分中探討分子內 Wittig 反應的化學選擇性,針對中間體上兩個不同的反應中心進行吲哚化合物與呋喃分子之選擇性合成。 第一部分:一個新的合成方法可針對 α,β-不飽和酮基之 β 位置進行直接的醯化反應。以 1,3-二茚酮烯類衍生物作為探討此反應之主要目標起始物,反應中使用催化量的膦試劑與醯氯反應,並且在三乙基胺試劑下可得到 β-醯化產物。多種醯氯試劑皆可良好的被應用於反應中並都擁有不錯的產率。除了多種 α,β-不飽和酮基皆可很好的被應用於反應中外,此合成策略也成功地延伸至 使用α,β-不飽和的酯基與醯胺基作為起始物中。另外,也將醯化產物繼續經由 hydazination 反應合成 pyridazine 產物。經由此二步反應,可有效率的合成出一個具有雜環的多環結構化合物。 第二部分:針對本實驗室所開發的分子內 Wittig 反應之化學選擇性進行探討。設計一個同時具有酯基與醯胺基之中間體,以分析分子內 Wittig 反應對於兩者間在生成吲哚化合物與呋喃分子之間的化學選擇性作探討。
This thesis is divided into two parts: direct β–acylation of 2-Arylidine-1,3-indandiones catalyzed by organophosphanes (part I), and synthesis of indoles and furans via chemoselective intramolecular Wittig reactions (part II). In the first part, we have developed a new synthetic method for β–acylation of 2-Arylidine-1,3-indandiones. In the reaction only catalytic amount of organophosphane was required to provide acylated products in up to 98% yield. Starting from various substituted 2-arylidene-1,3-indandiones and acyl chlorides in the presence of Et3N. Further application using acylated products as starting materials was also performed to afford pyridazine compounds in good yields. Compounds having indole framework are important for pharmaceutical aspect. In the second part, a developed protocol in our laboratory was utilized to synthesize indole compounds. In order to investigate the chemoselectivity of intramolecular Wittig reactions, we designed ylides as reactive intermediates with both ester and amide functionalities.

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β-醯化反應, 分子內 Wittig 反應, β-acylation, Intramolecular Wittig Reaction

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