臺灣博碩士論文加值系統

常見天然物中含有非常多靛紅衍生物，因此在這類的合成策略非常重要，將可應用在天然物的合成上。在本論文中，我們嘗試使用不同的三級膦與不對稱雙炔化合物和靛紅丙二腈進行反應，之後進行一連串的反應得到環化的產物。經過氫譜、碳譜、紅外線光譜、質譜和 X 光單晶繞射的鑑定其結構後，這些帶有伊立德結構的化合物利於具相同部位的全合成化合物的合成，為了提升對這類多組成反應的產率及探討其取代基的影響，我們嘗試著使用不同的反應條件與改變不同的反應物取代基。

Such synthetic methodology can be used to synthesize nature products because lots of nature compounds bear isatin skeleton. In this study, we try to used phosphine, (Z)-methyl 3-methyl-5-phenylpent-2-en-4-ynoate and isatyldene malononitrile derivative to obtain the cycloproducts bearing ylide functionality. We characterized these products by 1H NMR, 13C NMR, IR, Mass and X-ray diffraction analyses. These readily available structures may be advantageous to the total synthesis of molecules having this moiety. To optimize and discuss the substituent effects, we study reactions under different conditions.

摘要 I
ABSTRACT II
謝誌 III
第一章緒論 1
1.1有效合成有機反應 1
1.2 多組成反應 1
1.3多組成反應歷史 3
1.4多組成環化反應 6
1.4.1兩性離子的產生 6
1.4.2 DMAD反應研究 8
1.4.3 DMAD反應類型 8
1.4.4三級膦與DMAD的相關反應 9
1.4.5異腈與DMAD的相關反應 10
1.4.6 Carbene與DMAD相關反應 12
1.4.7 γ-丁內酯的多組成反應 16
1.4.8 γ-內醯胺的多組成反應 17
1.4 .9含氮雜環與DMAD相關反應 21
1.4.10 DMAD與靛紅反應合成螺旋化合物 23
1.4.11 DMAD與碳六十多組成反應 24
1.5不對稱炔類的多組成反應 25
1.6不對稱烯炔類的多組成反應 30
1.7多組成與靛紅衍生物反應 34
1.8螺環吲哚的應用 36
第二章 靛紅丙二腈、烯炔和三級膦的反應 40
2.1研究動機 40
2.2不對稱烯炔合成方法 41
2.3尋找最佳化條件 43
2.4不同官能基的反應探討 47
2.4.1反應流程 47
2.4.2靛紅衍生物探討 47
2.5產物4a及4a′的鑑定 51
2.5.1產物氫譜的鑑定 51
2.5.2產物碳譜的鑑定 52
2.5.3產物二維核磁共振光譜的鑑定 54
2.5.4產物紅外線光譜的鑑定 59
2.5.5產物X-ray單晶繞射分析的鑑定 60
2.6反應機構的探討 61
2.6.1攻擊在化合物1/2/3/4的α位 61
2.6.2攻擊在化合物1/2/3/4的β位 62
2.6.3攻擊在化合物1/2/3/4的γ位 64
2.6.4攻擊在化合物1/2/3/4的δ位 65
第三章 結論 69
參考文獻 70

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