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Author: 趙姿晴
Chao, Tzu-Ching
Thesis Title: 經由有機催化1,6-/縮醛化/1,4-連鎖反應合成三環苯併二氫吡喃之架構
Organocatalytic Synthesis of Tricyclic Chroman Scaffold via 1,6-/Acetalization/1,4- Reaction Sequence
Advisor: 陳焜銘
Chen, Kwun-Min
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2018
Academic Year: 106
Language: 中文
Number of pages: 138
Keywords (in Chinese): 有機催化共軛雙烯1,6-加成反應1,4-加成反應三環苯併二氫吡喃
Keywords (in English): organocatalytic, conjugated dien, 1,6-addition, 1,4-addition, tricyclic chromanes
DOI URL: http://doi.org/10.6345/THE.NTNU.DC.062.2018.B05
Thesis Type: Academic thesis/ dissertation
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  • 本文藉著使有具有拉電子基共軛雙烯化合物,及具有多反應位點之1-(2'-羥基苯基)丁烷-1,3-二酮,透過有機鹼活化下,進行1,6-/acetalization/1,4-加成連鎖反應,建立三環苯併二氫吡喃架構,且具有五個立體中心的產物,但其非鏡像選擇性不佳(1.6:1 dr);爾後,添加丁烯酮作為親電子性試劑,再進行1,4-加成反應,可使提升非鏡像選擇性(9:1 dr),有不錯的產率高達89%,且包含兩個四級碳的立體化學中心。此反應也可以進行一鍋化反應,利用雙烯、1-(2'-羥基苯基)丁烷-1,3-二酮及丁烯酮進行一鍋化1,6-/acetalization/1,4-/1,4-加成連鎖反應,也可以有好的產率74%,以及維持其非鏡像選擇性(9:1 dr)。然而,具有鏡像選擇性之產物,仍在進行探討研究中。

    An organic base catalyzed 1,6-/acetalization/1,4- cascade reaction between 1-(2'-hydroxyphenyl)butane-1,3-dione with many reactive sites and conjugated dien with strong electron withdrawing group leads to the formation of synthetically important tricyclic chromanes scaffolds bearing five stereogenic centers. However, the diastereoselectivities not well(1.6:1 dr). After that, with methyl vinyl ketone as electrophile reagent to 1,4-addition can improving diastereoselectivities(9:1 dr)in good yield(89%)and including two tetrasubstituted carbon stereogenic centers. This reaction was also put into the process of one pot directly from conjugated dien, 1-(2'-hydroxyphenyl)butane-1,3-dione and methyl vinyl ketone through efficient 1,6-/acetalization/1,4-/1,4- cascade reaction in well yield(74%)and maintain the diastereoselectivities(9:1 dr). Nevertheless, the enantioselectivity of product is still in study.

    第一章 緒論 1 1-1 前言 1 1-2 有機不對稱合成 5 1-3 有機催化劑 5 1-3-1 共價催化 8 1-3-2 非共價催化 11 1-4 1,4-加成反應 14 1-5 1,6-加成反應 15 1-6 有機不對稱連鎖反應 19 1-6-1 有機不對稱連鎖反應合成三環苯併二氫吡喃 22 1-7 研究動機 25 第二章 結果與討論 27 2-1 雙烯類化合物製備 27 2-2 三環苯併二氫吡喃之架構 28 2-3-1 有機催化劑的篩選 28 2-3-2 溶劑的篩選 31 2-3-3 添加劑篩選 33 2-3-4 最佳化條件篩選 34 2-3-5 取代基效應 35 2-3-6 一鍋化反應之探討 37 2-4 產物之結構分析 38 2-4-1 X-ray 單晶繞射結構分析 38 2-4-2 NMR 光譜解析 39 2-5 反應機構之探討 43 2-6 結論 44 第三章 實驗流程與數據 47 3-1 分析儀器及基本實驗操作 47 3-2 實驗步驟 49 3-3 光譜數據 51 第四章 參考文獻 63 附錄一 1H及13C-NMR光譜圖 65 附錄二 X-ray 結構解析與數據 113

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