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研究生:李文雄
研究生(外文):Wen-Hsiung Li
論文名稱:抗腫瘤天然物Goniotriol之合成研究
論文名稱(外文):Synthetic Study of Antitumor Goniotriol in Goniothalamus sesquipedalis
指導教授:黎世源黎世源引用關係沈建昌沈建昌引用關係
指導教授(外文):Shyh-Yuan LiChien-Chang Shen
學位類別:碩士
校院名稱:中國文化大學
系所名稱:應用化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:64
中文關鍵詞:不對稱合成抗腫瘤作用goniotriol
外文關鍵詞:asymmetricantitumorgoniotriol
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摘要
Goniotriol是從番荔枝科植物Goniothalamus sesquipedalis枝
葉中分離出來的天然物,屬於styryl lactone,具有5,6-dihydro-
2-pyrone之結構。天然界產生的6-substituted 5,6-dihydro-2-pyrone具有多種不同的生物活性,而研究顯示goniotriol對許多腫瘤細胞都有抑制作用,這引起了我們對其合成之興趣。
Goniotriol的合成我們先以methyl mandelate為起始物,將hydroxyl group用methoxymethyl ether保護起來,接著在-78℃下將ester以DIBAL還原成aldehyde。此aldehyde並不很安定,於是立即與methyl (triphenylphosphoranylidene)acetate在苯中進行Wittig
reaction。形成雙鍵之後,在t-BuOH-H2O (1:1) 中利用AD-mix-β進行Sharpless asymmetric dihydroxylation來氧化形成diol,此時利用矽膠管柱層析欲分離反應物與產物結果都失敗。嘗試多次後我們決定改用第二種方法。將ethyl 3-benzoylacrylate溶於苯中以p-TsOH為催化劑和ethylene glycol進行ketalization得到ketal產物,接著與AD-mix-β在t-BuOH-H2O (1:1)中進行Sharpless asymmetric dihydroxylation產生diol,再將此diol以methoxymethyl ether保護起來。然後在-78℃以DIBAL還原ester形成aldehyde;續與ethyl propiolate、ethylmagnesium bromide或lithium
diisopropylamide在THF中進行addition反應,但卻產生相當多的產物,難以分離,因此在nucleophilic addition反應中的方法還需要再進一步加以改進。

Abstract
Goniotriol was a styryl lactone isolated from the leaves and twigs of Goniothalamus sesquipedalis and was shown to be cytotoxic to several human tumor cells, which prompted us to study its synthesis.
We started the synthesis with methyl mandelate.After protection of the hydroxyl group with methoxymethyl ether, the ester was reduced by DIBAL to give the unstable aldehyde, which was immediately treated with methyl (triphenylphosphoranylidene)
acetate to give the Wittig product.However, it was unsuccessful to transform the double bond into the diol by Sharpless asymmetric dihydroxylation with AD-mix-β, so we attempted another approach with ethyl 3-benzoylacrylate as the starting material.It reacted with ethylene glycol in the presence of catalytic p-TsOH to afford a ketal, which was successfully dihydroxylated with AD-mix-β.The diol was protected with methoxymethyl ether and then the ester group was reduced by DIBAL to give an aldehyde, whereas the reaction of the aldehyde and ethyl propiolate with ethylmagnesium bromide or lithium diisopropylamide as the base yielded complicated products.
Therefore, the nucleophilic addition should be improved and other routes for the synthesis can be further considered.

目錄
中文摘要 Ⅰ
英文摘要 Ⅲ
壹、緒論 1
貳、儀器與藥品 10
參、研究方法 13
肆、實驗部分 17
伍、結果與討論 28
陸、參考文獻 30
柒、附錄 33

陸、參考文獻
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