輔仁大學
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學校名稱輔仁大學
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研究生(中)李澤明
研究生(英)Lee Tse-Ming
論文名稱(中)以環合歧化反應合成硫取代之吲啶與喹啶衍生物之研究
論文名稱(英)Synthetic Studies of Sulfur-substituted Indolizidines and Quinolizidines by Ring-Closing Metathesis
其他題名
指導教授(中)周善行
指導教授(英)Chou shang-shing Peter
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畢業學年度94
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關鍵字(中)衍生物 硫 環合歧化 氫原子 衍生物 化合物 甲苯 速率
關鍵字(英)quinolizidine
摘要(中)本論文利用環合歧化反應(RCM)合成出兩個新的?啶化合物 (quinolizidines)13與14。化合物10先轉換成11,再進行RCM生成化合物13。另外,化合物1a在C-2位置接上一2-methyl-2-propenyl的取代基得到化合物24,再與PTSI進行[4+2]環化加成反應合成出雙環化合物26,並進一步切除氮上甲苯?基,接上allyl 基後進行RCM反應,可得到甲基位置位於C-8位置的化合物14。我們比較了化合物13與14不同的生成速率,並推測其原因在於不同位置甲基和C-6的氫原子有不同程度的互斥。另外,我們也將化合物13氧化為22與23。
摘要(英)This thesis has accomplished synthesis of new quinolizidine compounds 13 and 14 by ring-closing metathesis (RCM). Compound 10 was first converted to compound 11 , which underwent RCM to give product 13. On the other hand, compound 1a was alkylated at C-2 to give 3-sulfolene 24, which was reated with PTSI to give the cycloaddition product 26. Upon cleavage of the N-tosyl group, and attachment of the allyl group, the intermediate product 12 also underwent RCM to give quinolizidine 14, but only at much higher temperature and with lower yield. It is proposed that in the rate-determining step the different positions of the methyl group in compounds 11 and 12 had different steric hindrance with the C-6 hydrogen. Compound 13 was further oxidized by m-CPBA to compounds 22 and 23.
論文目次中文摘要………………………………………………………i 英文摘要………………………………………………………ii 緒 論……………………….……………………………... 1 本論文研究重點……………..………………………...……..11 實驗結果與討論……………………………………..……….13 結 論………………………………………………….…..24 使用之儀器、藥品和溶劑………………………………………..26 實驗步驟與光譜數據…………………………………….…..29 參考文獻……………………………………………….….….45 附錄…………………………………………………….….….51
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