Total Synthesis of (±)-Panduratin D

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姓名

趙翊豪(I-hao Chao) 查詢紙本館藏

畢業系所

化學學系

論文名稱

(Total Synthesis of (±)-Panduratin D)

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摘要(中)

從凹唇薑(或稱高良薑)身上萃取出的(–)-panduratin D被檢驗在營養喪失的條件下，有些許抗人類胰腺癌細胞活性，然而至今沒有關於(–)-panduratin D的全合成文獻發表。我們以3-甲氧苯酚作為起始物，經由10步合成成功得到外消旋panduratin D。關鍵步驟包含使用鄰位陰離子夫裏士重排(anionic ortho-Fries rearrangement)及薗頭耦合合環(Sonogashira coupling annulation)反應來建構苯并呋喃的本體結構、鄰位定向硼酸鹽氧化反應、醯胺的烷化反應、醛醇縮合作用，以及最後在狄耳士-阿德爾反應後建立此化合物的立體中心。確定路徑後，我們在最後一步嘗試做狄耳士-阿德爾的不對稱反應來得到單一的鏡像異構物；我們也嘗試做羥基定向烷化反應取代親核性烷基鋰試劑的使用。

摘要(英)

(–)-panduratin D, isolated from Boesenbergia pandurate, was examined a mild activity against human pancreatic PANC-1 cancer cells under nutrient-deprived conditions. We first synthesized racemic panduratin D from 3-methoxyphenol in 10 steps. The key features included construction of benzofuran system by anionic ortho-Fries rearrangement and Sonogashira coupling annulation of 2-iodo-3-methoxyphenyl diethylcarbamate, directed ortho borate oxidation, alkylation of amide, aldol condensation, as well as Diels-Alder reaction, which established the stereocenter. Later, we tried some enantioselective Diels-Alder reactions expected to afford single enantiomer; we also tried applying hydroxyl-directed alkylation in place of alkylation with nucleophilic alkyl lithium reagent.

關鍵字(中)

★ 狄耳士-阿德爾反應
★ 羥基定向烷化反應

關鍵字(英)

★ panduratin D
★ Diels-Alder reaction
★ hydroxyl-directed alkylation

論文目次

中文摘要 i
Abstract ii
誌謝 iii
Catalog v
List of Schemes vii
List of Figures viii
List of Tables ix
Chapter 1 Introduction 1
Chapter 2 Results and Discussion 7
2-1 Retrosynthetic Analysis 7
2-2 Preparation Compound 15 as the Precursor of Benzofuran 16 9
2-2-1 Synthesis of Iodoarylcarbamate 12 10
2-2-2 Fries Rearrangement and Sonogashira Coupling 11
2-3 Benzofuran Annulation and Synthesis of Chalcone 16
2-3-1 Two ways to approach acetophenone 19 17
2-3-2 Synthesis of Chalcone 20 23
2-4 Panduratin D via Diels-Alder reaction 28
2-5 Enatioselective Diels-Alder reactions 33
Chapter 3 Conclusion 35
Chapter 4 Experimental Section 36
Total Scheme 51
References 52
Appendix 55

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指導教授

陳榮傑

審核日期

2015-1-30

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