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研究生： 陳雅佩
Chen, Ya-Pei
論文名稱： 氧釩金屬錯合物催化烯烴進行 1,2-氧化三氟甲基化反應之研究
Vanadyl Species-Catalyzed 1,2-Oxidative Trifluoromethylation of Unactivated Olefins
指導教授： 陳建添
Chen, Chien-Tien
口試委員: 林俊成
Lin, Chun-Cheng
吳學亮
Wu, Hsyueh-Liang
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2018
畢業學年度： 106
語文別： 中文
論文頁數： 202
中文關鍵詞： 氧釩金屬錯合物 、自由基加成 、氧化三氟甲基化反應
外文關鍵詞： vandyl species, radical type addition, β-trifluoromethylated ketones
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    • 過去本實驗室曾以氧釩金屬錯合物針對烯烴及醛類衍生物搭配第三丁基過氧化劑進行醯自由基加成氧化偶和反應，已有不錯的效果，且可針對 β-位進行過氧化和羰基化反應之選擇。
    本次研究中，我們開發了一種新的催化模式，用於 CF3 自由基加成至未活化之烯烴衍生物，並以 Togni's I 試劑作為 CF3 自由基之來源，生成各種 β-三氟甲基化酮類產物。我們使用不同的氧釩錯合物催化 Togni's I 試劑，並以氧氣為氧化劑，丙酮為溶劑於室溫下針對未活化之烯烴衍生物進行 1,2-氧化三氟甲基化反應，而其中 3,5-雙溴基取代之 N-亞柳第三丁亮氨酸氧釩錯合物與 VO(OTf)2 搭配雙牙噁唑啉配體之結果最佳，反應時間為 15-48 小時，產率介於 51-95% 。

    Previously, we have reported 1,2-hydroxy- or 1,2-peroxy acylation of olefins by using two different vandyl species with high efficiency in warm acetonitrile.
    Recently, we develop a new catalytic protocol for the “CF3“-radical type addition to unactivated olefins with Togni's reagent to deliver various β-trifluoromethylated ketones. A series of oxovanadium species were examined as catalysts for the 1,2-oxidative trifluoromethylation of styrene with Togni's reagent using oxygen as the sole oxidant at ambient temperature in acetone. In addition, various oxidovanadium complexes derived from N-salicylidene-tert-leucinate and SALEN were investigated, the complex with 3,5-dibromo substituents and VO(OTf)2 with bisoxazoline type ligands led to the best results, in 15-48 hours, in 51-95% yields.

    中文摘要 ..........................................................II Abstract..........................................................III 目錄..............................................................IV 式目錄............................................................VII 表目錄............................................................XIV 圖目錄............................................................XV 縮寫對照表........................................................XVI 第壹章、緒論.........................................................1 第一節、釩...........................................................1 第二節、氧釩錯合物在有機合成及催化反應之應用............................3 1.氧釩錯合物催化烯類化合物之環氧化反應.................................3 2.氧釩錯合物催化二級醇類化合物進行之不對稱氧化反應.....................10 3.氧釩錯合物催化芳香酚類化合物進行之不對稱偶合反應.....................16 4.氧釩錯合物催化硫醚類化合物進行之不對稱氧化反應.......................22 5.氧釩錯合物進行之不對稱氰醇或醛醇加成反應............................28 第貳章、N-亞柳胺基酸衍生掌性氧釩錯合物催化烯烴類衍生物進行氧化三氟甲基化反應 32 第一節、前言與文獻探討...............................................32 1.碳碳雙鍵交聯偶合反應...............................................32 2.三氟甲基的加成與衍生反應...........................................35 3.研究動機..........................................................41 第二節、結果討論....................................................43 1.不同氧釩金屬鹽類對烯烴進行氧化三氟甲基化反應之結果 ...................43 2.不同自由基促進劑對烯烴進行氧化三氟甲基化反應測試之結果................47 3.不同溶劑對烯烴進行氧化三氟甲基化反應之結果...........................49 4.不同N-亞柳胺基酸氧釩錯合物對烯烴進行氧化三氟甲基化反應之結果..........52 5.不同烯烴衍生物對氧化三氟甲基化反應之結果............................54 6.反應機構之探討與研究...............................................57 7.結論與未來展望....................................................59 第參章、分析儀器、實驗步驟及光譜數據..................................60 第一節、分析儀器....................................................60 第二節、實驗步驟與光譜分析...........................................63 1.N-亞柳胺基酸與 N-柳胺基酸衍生之掌性釩氧錯合物合成步驟與光譜數據.......63 2.氧釩金屬鹽製備之反應步驟...........................................69 3.不同氧釩金屬鹽類對苯乙烯進行氧化三氟甲基化反應.......................72 4.VO(OTf)2 與添加劑對苯乙烯進行氧化三氟甲基化反.......................78 5.不同自由基促進劑對烯烴進行氧化三氟甲基化反應.........................88 6.不同溶劑對烯烴進行氧化三氟甲基化反應之結果...........................95 7.不同N-亞柳胺基酸氧釩錯合物對烯烴進行氧化三氟甲基化反應...............104 8.烯烴衍生物之氧化三氟甲基化反應.....................................108 參考文獻...........................................................115 附錄1、1H NMR、13C NMR、19F NMR與51V NMR光譜圖......................S1

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