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研究生: 林育賢
Lin, Yu-Sian
論文名稱: 高度非鏡像選擇性有機催化[2+2+2]環化反應合成全取代螺環吲哚酮
Highly Diastereoselective Synthesis of Fully Substituted Spirocyclic Oxindole via Organocatalysis [2+2+2] Annulation Reaction
指導教授: 陳焜銘
Chen, Kwunmin
口試委員: 陳焜銘
Chen, Kwunmin
杜玲嫻
Tu, Ling-Hsien
李文山
Li, Wen-Shan
口試日期: 2022/07/26
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2022
畢業學年度: 110
語文別: 中文
論文頁數: 94
中文關鍵詞: 有機催化連鎖反應螺環吲哚酮
英文關鍵詞: cascade, spirocyclic oxindoles
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202200966
論文種類: 學術論文
相關次數: 點閱:107下載:17
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  • 此論文成功開發全取代螺環吲哚酮衍生物的合成方法,並且得到兩個四級碳中心,透過有機催化連鎖反應,進行 Michael/Michael/1,2-addition 反應。在 0 ℃的條件下,使用丙二腈、苄烯丙二腈、(E)-3-苄基-1-叔丁氧羰基-2-吲哚酮作為起始物,並以乙腈作為溶劑,加入催化量(30 mol%)的四甲基乙二胺,反應 8到 20 小時,製備全取代螺環吲哚酮衍生物,得到中等到良好的產率(45 - 81 %)、良好的非鏡像選擇性(14:1 - >20:1 d.r.)。

    An efficient cascade protocol between malononitrile, benzylidenemalononitrile, and (E)-tert-butyl-3-benzylidene-2-oxoindoline-1-carboxylate has been developed. Fully substituted spirocyclic oxindole derivative bear two all-carbon quaternary centers. The reaction proceeds through a Michael/Michael/1,2-addition reaction. The spirocyclic oxindole derivatives were obtained in reasonable-to-good chemical yields (45 - 81 %) and high levels of diastereoselectivities (14:1 - >20:1 d.r.) using a catalytic amount of commercially available TMEDA (30 mol%) in ACN at 0 ℃ for 8 - 20 h.

    目錄 簡歷i 謝誌ii 摘要iii Abstractiv 目錄v 圖目錄vii 表目錄ix 第一章 緒論1 1-1 前言1 1-2 有機催化連鎖反應6 1-2-1 Domino 反應8 1-2-2 Cascade 反應14 1-2-3 Tandem 反應18 1-3 螺環吲哚酮20 1-4 本實驗室在有機催化連鎖反應暨螺環衍生物之研究24 1-5 研究動機26 第二章 研究結果與討論27 2-1 有機催化連鎖反應暨螺環吲哚酮之合成27 2-2 有機催化連鎖[2+2+2]環化反應28 2-2-1. 路易士鹼催化劑之篩選28 2-2-2. 反應溶劑之篩選29 2-2-3. 反應濃度與反應時間之篩選31 2-2-4. 催化劑使用量之篩選32 2-2-5. 反應溫度之篩選33 2-2-6. 當量數之篩選33 2-2-7. 取代基效應35 2-3 全取代螺環吲哚酮之結構鑑定與解析36 2-4 反應機構探討44 2-5 結論48 第三章 實驗部分49 參考文獻59 附錄一63 附錄二80

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