壹、不飽和系統化合物：加成反應之開發與探討 貳、多組成反應的應用：色烯類衍生物的合成 參、一鍋化合成異噁唑類衍生物：三聚氰氯作為脫水劑

I.Unsaturated Compound System : The Study of the Addition Reaction II.The Application of the Multicomponent Reaction : The Synthesis of Chromene Derivatives III. One-Pot Synthesis of Bicyclic Isoxazole Derivatives : Cyanuric Chloride as Dehydrating Agent

高士杰(Shijay Gao)

指導教授 ： 姚清發

國立臺灣師範大學/理學院/化學系/博士(2009年)

摘要

本論文共分成三部分

第一部分：文獻中使用未具有保護基的α,β-不飽和羧基化合物進行加成反應時通常都獲得較低的產率，推測可能原因是因為α,β-不飽和羧基化合物的反應性較低與羧基官能基可能會參與反應或是破壞反應進行導致產率下降。當以碘(I2)或四丁基氟化銨(TBAF)作為催化劑時，使用硫醇作為親核性試劑與α,β-不飽和羧基化合物進行加成反應，經由簡單的條件控制即可獲得高產率的硫加成產物。上述的研究過程中，我們意外發現一個新穎且高效率的合成路徑，快速且簡單的合成3-(1-(thio)ethyl)-1H-indole衍生物。

第二部分：色烯類化合物具有多樣的生物活性以及在醫藥上廣泛的應用，引起化學家對色烯類化合物的研究與探討，我們利用多組成反應策略發展出一個符合綠色化學精神的色烯類化合物合成方法，此方法具有簡短的合成步驟、可回收、高效率、操作方便、高產率與僅需少數反應物即可獲得多種衍生物等優點。

第三部分：噁唑類化合物廣泛存在於許多天然物的結構中，異噁唑類化合物經由不同的還原條件可將氮-氧單鍵轉換合成出一系列1,3位置具有不同官能基的化合物。異噁唑類化物在有機合成上的價值，引起化學家對異噁唑類化物的研究與探討。我們以三聚氰氯作為脫水劑，以一鍋化的反應條件合成多環系統的異噁唑類化合物。此方法具有簡短的合成步驟、高效率、高產率獲得多環系統的異噁唑類化合物等優點。

關鍵字

加成反應 ； 多組成反應 ； 色烯類衍生物 ； 異噁唑類衍生物 ； 三聚氰氯

並列摘要

In the first part of this dissertation, we have developed a novel procedure for the synthesis of 3-sulfanylpropionic acid in excellent yields. The iodine (I2) and tetrabutylammonium fluoride (TBAF) could be applied successfully to a variety of α,β-unsaturated carboxylic acids as well as thiols to synthesize a wide variety of sulfur containing carboxylic acids in excellent yields. Furthermore, the synthesis of novel 3-(1-(thio)ethyl)-1H-indole derivatives was also described.

The second part focuses on the use of the recyclable fluoride ion to catalyze the multicomponent reactions for the synthesis of 4H-chromene and N-quinoline derivatives, which are often encountered in molecules of biologically active compounds. The multicomponent reaction strategy affords savings in synthetic time and effort, and has significant advantages over conventional two-component reactions in several aspects, such as variable and high bond forming efficiency.

Finally, we have developed a novel procedure for the one-pot synthesis of isoxazolines and isoxazoles. The procedures described here are simple and efficient. The use of 2,4,6-trichloro-1,3,5-triazine (TCT) as a dehydrating agent has the advantages of being economically viable and more efficient for the conversion of nitronate into nitrile oxide. The reaction system can be applied successfully to a variety of nitroalkenes as well as nucleophiles to synthesize various bicyclic isoxazolines and isoxazoles, and tricyclic products.

並列關鍵字

Addition Reaction ； Multicomponent Reaction ； Chromene Derivatives ； Isoxazole Derivatives ； Cyanuric Chloride

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