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研究生: 趙希德
論文名稱: 以碳為中心之路易士酸及其在醛醇反應之應用
指導教授: 陳建添
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
畢業學年度: 85
語文別: 中文
論文頁數: 114
中文關鍵詞: 非鏡像立體選擇性
英文關鍵詞: diastereoselectivities
論文種類: 學術論文
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  • 以Dibenzosuberone為模板,與格里納(Gringnard)或有機鋰試劑的加成反應,我們設計了一系列具有不同官能基取代的三芳香基甲基醇類化合物,再利用Williamson ether synthesis 方法合成三芳香基甲基甲基醚類化合物,我們已成功發展出一新的親電子性離子化方法,在三種不同種類的Meerwein salts (Me3O+SbCl6-, Et3O+BF4-, Et3O+PF6-)中,將甲基醚轉換成三芳香基碳陽離子。在以HPLC的追蹤中,以Me3O+SbCI6-較能有效的生成trityl salts, 並且首次利用在Mukaiyama醛醇加成反應上;在這個系統上,能成功的壓抑住矽烷基形態的競爭催化效應,得到相當好的非鏡像立體選擇性(syn/anti 90/10至>95/5)。
    而更進一步的,我們已合成出在10,11位置上具有甲基或乙基取代等具有C2對稱性的對掌性化合物,利用酸或Meerwein salts的離子化方式生成chiral trityl salts,藉著碳陽離子具有的路易士酸特性,首次成功地利用在不對稱Mukaiyama醛醇加成反應上,其鏡像立體選擇性。(enantiomeric excess, e.e)可達38%,而以一個當量催化時e.e值可至50%,相信我們的研究,可帶給人家一新領域的擴展空間。

    We have devised a general and efficient synthesis of various triarylcarbenium ions bearing functionalized aryl groups.The requisite trityl alcohol precursors synthesized by addition of the respective aryllithium or arylmagnesium bromide to dibenzosuberone were first methylated to the corresponding methyl ethers by Williamson ether synthesis in 70 to 97% yields.Three different Meerwein salts (Me3O+SbCl6-, Et3O+BF4-, and Et3O-+PF6-) were employed to ionize the respective trityl methyl ethers into the corresponding triarylcarbenium ions.Hexachloroantimonates were found to be the most complete and efficient analogs in these three cases as judged by HPLC analysis of the resulting alcohols after aqueous workup.We have demonstrated, for the first time, that triarylcarbenium hexachloroantimonates can serve as effcient catalysts to fulfill the Mukaiyama aldol reactions with negligible intervention of silyl catalysis.The aldol addition between silyl ketene acetal derived from r-butyrolactone and benzaldehyde provided the silyl aldolates with good to high diastereoselectivities (syn/anti, 90/10 to >95/5).
    We also have devised an efficient synthesis of various chiral triarylcarbenium ions bearing functionalized aryl groups by acid- or Meerwein-promoted ionization of the corresponding trityl alcohols or trityl methyl ethers.The requisite trityl alcohol precursors were synthesized by addition of the respective aryllithium to C2-symmetric 10, 11-dimethyl and diethyl-dibenzosuberones, readily available in 3 steps from the known 10, 11-bis(methyl ester) analog, We have attempted the first chiral trityl ion-mediated Mukaiyama aldol addition.Our first targeted aldol addition involves the addition of O-ethyl silyl ketene acetal to benzaldehyde.This most challenging scenario documented in previous catalytic asymmetric aldol reaction was found to proceed smoothly leading to enantiomerically enriched ethyl 3-hydroxy-3-phenylpropionate with up to 50% ee.

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