簡易檢索 / 詳目顯示

研究生: 吳冠杰
Wu, Guan-Jie
論文名稱: 由碘介導甲醇/乙醇間斷異-納札羅夫環化反應之共軛二烯以獲得高取代性之二烷氧基環戊烯衍生物
Iodine-Mediated Methanol/Ethanol Interrupted Iso-Nazarov Reaction of Conjugated Dienals for Accessing Highly Substituted Dialkoxy Cyclopentene Derivatives
指導教授: 姚清發
Yao, Ching-Fa
口試委員: 林文偉
Lin, Wen-Wei
柳如宗
Liu, Ru-Zhong
姚清發
Yao, Ching-Fa
口試日期: 2022/06/17
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2023
畢業學年度: 111
語文別: 中文
論文頁數: 180
中文關鍵詞: 納札羅夫反應二烯醛微波合成儀
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202301298
論文種類: 學術論文
相關次數: 點閱:52下載:1
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報
  • 在1942年,科學家發現了納札羅夫(Nazarov)反應。然而在接下來的近八十年中,由於對其合成意義缺乏認識,這個反應並未受到太多關注。直到過去十年才有大量的研究被報導出來,原因在於此反應對於天然化合物或醫藥分子中所含的五圓環衍生物而言,是個十分有效的合成途徑。
    本研究即是以納札羅夫(Nazarov)反應的延伸 :「間斷異-納札羅夫(Interrupted Iso-Nazarov)」進行研究,探討不同溶劑作為親核劑在合環時產生的加成反應。使用二烯醛(Dienals)架構的分子與碘作為催化劑,搭配不同溶劑進行間斷異-納札羅夫合環反應,並利用聚焦式微波合成儀將反應時間大幅縮短,同時提升反應產率。利用親核基捕捉環戊烯中間體 ,進一步從結果探討捕捉加成時的不同立體位向,最終得到高度立體選擇性的不同取代基之二烷氧基環戊烯衍生物。

    Scientists have discovered the “Nazarov reaction” almost eighty years ago. However, for almost eighty years, it didn't receive much attention due to a lack of recognition regarding its synthetic significance. It was only in the past decade that a substantial amount of research has been reported, as this reaction has proven to be a highly effective synthetic pathway for pentacyclic derivatives found in natural compounds and pharmaceutical molecules.
    This research is an extension of the Nazarov reaction, which is "Interrupted Iso-Nazarov". The goal of the study is to investigate the addition reaction of different solvents as nucleophilic groups during the cyclization. We carried an iodine-catalyzed "interrupted iso-Nazarov" reaction of dienals in various solvents. Furthermore, we used "Microwave reactor" to substantially reduce reaction time and boost the yield of products. We attempted to use the nucleophile to trap the cyclopentene intermediate and further explored the different stereo orientations when trapping the intermediate from the results. Fortunately, highly stereoselective cyclopentene derivatives with different substituents were finally obtained at the end.

    謝誌 i 摘要 v Abstract vi 1 前言 1 1-1 納札羅夫(Nazarov)反應介紹 1 1-2 異-納札羅夫(Iso-Nazarov) 反應介紹 1 1-3 間斷異-納札羅夫(Interrupted Iso-Nazarov)反應介紹 2 2 文獻回顧 3 3 研究目標 10 4 實驗結果與討論 11 4-1 反應的發現與優化 11 4-1-1 甲醇作為溶劑產率優化 14 4-1-2 以乙醇為溶劑進行產率優化 16 4-2 化合物取代基效應的探討 17 4-2-1 在最佳化條件,以甲醇作為溶劑的不同取代基嘗試 17 4-2-2 在最佳化條件,以乙醇作為溶劑的不同取代基嘗試 22 4-3 反應機構的探討 28 5 結論 29 6 實驗方法 30 6-1 分析儀器及基本實驗操作 30 6-2 實驗步驟 33 7 參考文獻 35 8 光譜資料 37 8-1 NMR 38 8-2 單晶繞射X-Ray分析結構圖 58 9 1H-NMR及13C-NMR光譜附圖 104

    Nazarov, I. N.; Kuznetzova, A. I. Izv. Akad. Nauk SSSR, 1942, 392-405
    Riveira, M. J.; Marsili, L. A.; Mischne, M. P. Org. Biomol. Chem. 2017, 15, 9255-9274
    Yadykov, A.V.; Shirinian, V. Z. Adv. Synth. Catal. 2020, 362, 702-723.
    Alajarin, M.; Ballester, F.-J.; Vivancos, J.-A.; Orenes, R.-A.; Vidal, A.; Sanchez-Andrada, P.; Marin-Luna, M. J. Org. Chem. 2020, 85, 4565-4573.
    Ramesh, G.; Balamurugan, R. J. Org. Chem. 2021, 86, 16278-16292
    Marques, A.-S.; Coeffard, V.; Chataigner, I.; Vincent, G.; Moreau, X. Org. Lett. 2016, 18, 5296-5299.
    Marques, A.-S.; Marrot, J.; Chataigner, I.; Coeffard, V.; Vincent, G.; Moreau, X. Org. Lett. 2018, 20, 792-795.
    Marques, A.-S.; Duhail, T.; Marrot, J.; Chataigner, I.; Coeffard, V.; G. Vincent, X. Moreau. Angew. Chem. Int. Ed. 2019, 131(29), 10074-10078.
    Riveira, M. J.; Quiroga, G. N.; Mata, E. G.; Gandon, V.; Mischne, M. P. J. Org. Chem. 2015, 80, 6515-6519.
    1Riveira, M. J.; Mischne, M. P. An. J. Org. Chem. 2014, 79, 8244-8254.
    Riveira, M. J.;Marcarino, M.O.; La-Venia, A. Org. Lett. 2018, 20, 4000-4004.
    Lin, C.-C.; Teng, T.-M.; Odedra, A.; Liu, R.-S. J. Am. Chem. Soc. 2007, 129, 3798-3799.
    Lin, C.-C.; Teng, T.-M.; Tsai, C.-C.; Liao, H.-Y.; Liu, R.-S. J. Am. Chem. Soc. 2008, 130, 16417-16423.
    William, R.; Wang, S.; Ding, F.; Arviana, E. N.; Liu, X.-W. Angew. Chem. Int. Ed. 2014, 53, 10742-10746.
    William, R.; Leng, W. L.; Wang, S.; Liu, X.-W. Chem. Sci. 2016, 7, 1100-1103.
    Bandi, V.; Kavala, V.; Konala, A.; Hsu, C.-H.; Villuri, B. K.; Reddy, S. R.; Lin, L.-C.; Kuo, C.-W.; Yao, C.-F. J. Org. Chem. 2019, 84, 3036-3044.
    Hoff, B. H. Acetonitrile as a Building Block and Reactant. Synthesis. 2018, 2824-2852.
    Chen, M.-E.; Chen, X.-W.; Hu, Y.-H.; Ye, R.; Lv, J.-W.; Li, B.; Zhang, F.-M. Org. Chem. Front., 2021, 8, 4623-4664.

    下載圖示
    QR CODE