臺灣博碩士論文加值系統

b-取代的羰基化合物(b-Substituted Carbonyl Compound)為有機合成步驟中之重要中間物，它可以進一步轉換成許多天然物及藥物的重要骨架，如：b-羥基酮、b-羥基酯、b-胺基酸、b-內醯胺….等。目前文獻報導b-取代的羰基化合物之合成方法有：縮醛型式反應(Aldol-type Reaction) 、有機銅加成反應(Organocopper Addition Reaction)、麥克加成反應(Michael Addition Reaction)….等。這些反應常需先製備銅酸鹽(Cuprate)或烯醇(Enolate)與醛、酮或醯胺反應生成b-取代的羰基化合物。而合成b-取代羰基化合物的步驟過於繁瑣，而且製備有機金屬試劑有許多反應上的限制，降低其在有機合成上的實用性。我們將一系列的烯丙基酮(b,g-Unsaturated Ketone)與定當量的路易士酸(BF3‧OEt2)置於溶劑甲醇下，於室溫攪拌可得高幾何選擇性的b-甲烷氧基酮產物。若將烯丙基酮與定當量的路易士酸(AlCl3)及定當量的胺(Ts-NH2)在溶劑二氯甲烷下，於室溫攪拌可得高幾何選擇性的b-胺基酮產物。我們實驗室研發的方法為一溫和且簡捷的b-胺基酮及b-甲烷氧基酮合成反應，此高幾何選擇性的合成方法與策略可更進一步地擴充應用於不對稱合成反應和合成天然物及藥物。

Conjugate addition of organometallic reagent to a,b-unsaturated carbonyl compound is an important tool for specific introduction of a substituent to the b-position of carbonyl functionality. Synthetic methodologies for synthesis of b-substituted carbonyl compound are typically produced by the additional reactions such as Aldol-type reaction, organocopper addition reaction, and Michael addition reaction. However, the coexistence of addition metal salts and organic or inorganic compounds acting as promoters of the conjugated addition makes the reaction system complex, hampering the synthetic utility. Therefore, we developed a novel and mild synthetic method for the synthesis of b-substituted ketone. b-Methoxy ketones are synthesized by the reaction of b,g-unsaturated ketone with anhydrous methanol in the presence of BF3．OEt2 . The synthesis of toluenesulfonyl-amino ketones are achieved by the reaction mixture of b,γ-unsatutrated ketone, Ts-NH2 and AlCl3 in dry CH2Cl2 .

第一章 緒論……………………………………………………………….1
1-1 b-烷氧基與b-胺基羰基化合物的重要性…………………………2
1-2 b-取代羰基化合物的合成方法……………………………………8
1-2-1 縮醛型式反應(Aldol-type Reaction)…………………………..8
1-2-2 有機銅加成反應(Organocopper Addition Reaction)…………18
1-2-3 麥克加成反應(Michael Addition Reaction)………………… 23
1-3 b-甲氧基酮之合成方法……………………………………………25
1-4 b-胺基酮之合成方法………………………………………………28
第二章結果與討論……………………………………………………….30
2-1 路易士酸促進幾何選擇性加成反應合成b-甲氧基酮……………30
2-2 路易士酸促進幾何選擇性加成反應合成b-胺基酮………………35
2-3 反應機構的探討……………………………………………………38
第三章實驗與儀器……………………………………………………….42
3-1 實驗步驟…………………………………………………………….42
3-2 溶劑的乾燥………………………………………………………….44
3-3 實驗儀器與測試方法……………………………………………….45
第四章 總結………………………………………………………………48
第五章 光譜………………………………………………………………50
第六章 參考資料…………………………………………………………80

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