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研究生: 趙希德
Shi-Deh, Chao
論文名稱: 以官能化三芳香基甲基氯催化烯丙基化反應之探討
指導教授: 陳建添
Chen, Chien-Tien
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
論文出版年: 2001
畢業學年度: 89
語文別: 中文
中文關鍵詞: 三芳香基甲基碳陽離子烯丙基化反應
英文關鍵詞: Trityl ions, allylation, mukaiyama aldol reaction
論文種類: 學術論文
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  • 我們已合成出多種含五類環外芳香基,其中以二芐環庚烯[DBS] 為骨架之芳香基甲基氯化物,在鹵烷類溶劑中呈現最適當的離子強度,因而在TBSCl, TMSCl, RC(O)Cl 的促進劑作用下可催化醛與烯丙基第三丁基錫烷 (Allyltri-n-butyltin) 之間的烯丙基化反應。 不像三苯甲基 (Triphenylmethyl)、二苯並砒喃 (dibenzopyrane) 和茀 (fluorine) 所衍生的氯化物,其中以DBS 為骨架之氯化物可與烯丙基化試劑共存而不被消耗,每個例子皆可得到很好的產率。 我們更進一步以對照和轉換實驗來首度證明以DBS為骨架的芳香基甲基氯化物在烯丙基化反應中為真正的催化劑,而且只有非常輕微的矽烷氯化物的競爭催化。 並加以應用在以酮類為起始物的烯丙基化反應上,Aldimine addition, Mukaiyama Aldol reaction等不同的有機反應上,我們更成功合成出以二芐環庚烯 [DBS] 為骨架之手性芳香基甲基氯化物,並由X-ray結晶繞射圖的資訊上得知應用在非對稱合成上所須改進的部份。

    DRS-based model system exhibits moderate ionic characters, in alia, in halogenated solvents, thus serving as efficient catalysts in allylation reactions between aldehydes and allyltri-n-butyltin in the presence of TBSCl, TMSCl, Acroyl chloride promoter. In all cases, the resulting homoallylic alcohols were furnished in good yields (77-97%) with various substrates and stannanes. Control and turn-over experiments of trityl ether with TMSCl and acetyl chloride support, for the first time, the catalytic role of DBS-based trityl chlorides in the allylation reaction with negligible intervention of silyl catalysis. We also used it in the Aldimine addition and Mukaiyama Aldol reaction. We have succeeded in making chiral 10,11-tetrahydroflurano-diberzosubrane (DBS)-based trityl-type alcohol and, from its X-ray analysis data, we hope we can get good results in the asymmetric allylation in the future.

    中文摘要………………………………………………………………………………1 英文摘要………………………………………………………………………………2 第一章 緒論 第一節 前言及背景…………………………………………………………………..3 第二章 結果與討論 第一節 三芳香基甲基氯的合成及其離子特性探討………………………………..7 第二節 以三芳香基甲基氯應用於醛類之烯丙基化反應…………………………..9 第三節 以醯氯為促進劑進行烯丙基化反應之研究………………………………16 第四節 反應機制及催化途徑之探討………………………………………………19 第五節 轉換步驟之化學動力學研究………………………………………………20 第六節 以各式不同錫烷做為親核試劑應用於烯丙基化反應……………………26 第七節 以三芳香基甲基氯應用於酮類之烯丙基化反應…………………………30 第八節 以三芳香基甲基氯應用於亞胺類之烯丙基化反應………………………31 第九節 具掌性三芳香基甲基鹽的合成及在非對稱合成上應用與探討…………33 第十節 結論…………………………………………………………………………38 第十一節 參考文獻…………………………………………………………………39

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