臺灣博碩士論文加值系統

論文提要內容：
a,b-不飽和羰基化合物(a,b-Unsaturated Carbonyl Compound)在有機合成中扮演重要角色，可與親核子(Nucleophile)或親電子(Electrophile)進行反應生成有機合成中重要的前趨物，亦為許多天然物的重要基本架構。發展合成b-取代羰基化合物方法是有機化學家極感興趣的方向，它為有機合成步驟中的重要中間物，更為許多天然物和藥物之基本架構，廣泛地應用在化學醫藥領域上。通常合成b-取代羰基化合物的步驟過於繁瑣，所以我們實驗室發展出一溫和且簡捷的合成方法，成功地合成一系列b-取代羰基化合物。我們將一系列的烯丙基酮(b,g-Unsaturated Ketone)
與定當量的1,4-Diazabi-cyclo[2.2.2]octane(DABCO)在溶劑異丙醇(iPrOH)下，於室溫下反應生成一系列的a,b-不飽和酮(a,b-Unsaturated Ketone)，我們再將這一系列的a,b-不飽和酮、親核基(胺類或醯胺類化合物)與定當量的路易士酸於室溫下攪拌進行麥克加成反應(Michael Addition)，可生成1,4-加成的b-胺基酮或b-醯胺基酮化合物。

Abstract：a,b-Unsaturated carbonyl compound plays an important role in organic chemistry. The reaction products of a,b-unsaturated carbonyl compounds to either nucleophiles or electrophiles under reaction conditions have made them ideal precursors for organic synthesis and numerous natural products. The development of novel synthetic method leading to b-substituted carbonyl compound has received much attention in organic synthesis. The b-substituted carbonyl compound is an important intermediate for organic synthesis and an attractive target for natural products. The b-substituted carbonyl moiety is commonly observed in a large variety of biologically active compounds because of their prevalence and wide utility for organic chemistry.Therefore, we developed a novel and mild synthetic method for the synthesis of a,b-unsaturated ketone, b-amino ketone and b-amido ketone. The isomerization of a series of b,g-unsaturated ketones to their corresponding a,b-unsaturated ketones were achieved. The synthesis of b-amido ketones were obtained by the reaction of a,b-unsaturated ketones and Bz-NH2 in the presence of Me3SiOTf.

第一章 緒論 ………………………………………………………… 1
1-1 b-胺基與b-醯胺基羰基化合物的重要性 ……………….…… 2
1-2 b-胺基與b-醯胺基羰基化合物的合成方法 …………………10
1-2-1 b-胺基羰基化合物的合成方法………………………….. 10
1-2-1a 曼尼希縮合反應(Mannich Reaction) …………………10
1-2-1b 麥克加成反應(Michael Addition) …………………… 12
1-2-2 b-醯胺基羰基化合物的合成方法……………………….. 18
1-3 a,b-不飽和羰基化合物的應用與合成方法 ………………….. 21
1-3-1 a,b-不飽和羰基化合物在有機合成上的應用 ………... 21
1-3-1a 麥克加成反應 …………………………………….. 21
1-3-1b 狄爾斯-阿爾德反應(Diels-Alder Reaction) ……….. 29
1-3-1c a,b-雙取代羰基化合物 ……..….…………………. 32
1-3-2 a,b-不飽和羰基化合物之合成方法 ….………………... 39
1-4 b,g-不飽和酮異構化生成a,b-不飽和酮的方法 ……………… 41
1-4-1 酸性條件 ….……….…………………………………….. 41
1-4-2 鹼性條件 ……….…………….………………………….. 43
1-4-3 過渡金屬錯合物催化 ……..…………………………….. 46
第二章 結果與討論 ….……..……………………………………….. 47
2-1 b,g-不飽和酮之異構化 ………………………..……………… 47
2-2 路易士酸促進麥克加成反應合成b-胺基酮 …..……….…….. 54
2-3 路易士酸促進麥克加成反應合成b-醯胺基酮 ………...….…. 58
第三章 實驗與儀器 …………..…………………………….….. 67
3-1 實驗步驟 ……………..……………………………….…. 67
3-2 溶劑的乾燥 ………..………………………………….…. 70
3-3 實驗儀器與測試方法 …..…………………………….…. 71
第四章 總結 …..……….………………………………….….. 73
第五章 光譜 ………...………………………………………... 74
第六章 參考資料 ……..……………….………………………. 127

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