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    題名: (1) 設計並合成Acaterin及其衍生物、(2) Endo-Glycals 立體選擇性之醣加成反應;(1) Design and synthesis of (-)-Acaterin derivatives 、(2) Stereoselective Glycosylation of endo-Glycals
    作者: 吳旭軒;Hsu-Hsuan Wu
    貢獻者: 中國醫藥大學:藥物化學研究所碩士班
    關鍵詞: 乙醯基轉移酶;抑制劑;醣加成反應;Acaterin;2-deoxy glycosides;beta-enamino ketones
    日期: 2009-06-19
    上傳時間: 2009-08-13 09:37:26 (UTC+8)
    摘要: 目標化合物Acaterin (1)的合成可大致分為兩個片段,利用市售藥品Methyl acrylate與甲醛進行Baylis-Hillman反應得到第一片段,同時也用Methyl (S)-(-)-lactate進行Wittig反應得到第二片段;而本實驗室已將兩片段合成出,目前正進行Mitsunobu反應以及Grubbs catalyst將此兩片段接合起來,來得到Acaterin的內酯。
    此外,根據文獻報導,目前新方法合成2-deoxy glycosides是由hex-1-en-3-uloses當作起始物,利用路易士酸為催化而得;而本實驗室利用AlCl3?n當作催化劑,在微波反應條件下,可得到高產率、高立體選擇性的2-deoxy glycosides,同時???n: ???n的比例超過?n???~?n???n?﹛C
    最後,本實驗將endo-glycal利用PhI(OH)OTs氧化試劑得到開環產物,並且利用一鍋化反應,同時加入胺類,來得到??-enamino ketones。

    The intermediate compounds was synthesized by Baylis-Hillman reaction to couple acetaldehyde and the compound 13. We also used the starting compound 27 followed by reduction and Wittig rection to affored the intermediate compounds (E)-46, (Z)-46. The further works will be finished by Mitsunobu and Grubbs catalysis reaction to give to major compound 23.
    A new method for synthesis of ??-2-deoxyglycosides from hex-1-en-3-uloses is reported, hex-1-en-3-uloses were shown to be efficient glycosyl donors by using catalyst amount of AlCl3 in microwave-assisted glycosylation. In these reaction ??-glycosyl additions occurred with highly stereoselectivity (??:??=10:1).
    Fully protected endo-glucals are directly converted into compound 104, 105 by 1eq PhI(OH)OTs, followind addition amino in methanol at room temperature for 30 mins to affored the ??-enamino ketones.This sequestration reaction occurs in two steps which were studied separately and in a one-pot rection.
    顯示於類別:[藥物化學研究所] 博碩士論文

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