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Author: 曾秉曜
Tseng, Ping-Yao
Thesis Title: 一、透過鹼控制高醯基香豆素與 1,3-茚二酮衍生物進行化學選擇 性 1,6-Addition/Aldol 或 1,6-Addition/Michael 連續反應合成 香豆素衍生物 二、透過有機膦試劑、酸酐與亞芳基-1,3-茚二酮合成茚並 [1,2-c]呋喃衍生物
1.Divergent Synthesis of Coumarin Derivatives via Basecontrolled 1,6-Addition/Aldol and 1,6-Addition/Michael Cascades 2.Synthesis of Unprecedented Indeno[1,2-c]furan from αarylidene-1,3-indandione via Intramolecular Wittig Reaction
Advisor: 林文偉
Lin, Wen-Wei
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2019
Academic Year: 107
Language: 中文
Number of pages: 280
Keywords (in Chinese): 高醯基香豆素 、多樣性導向合成 、1,6-加成 、串聯反應 、茚並[1,2-c]呋喃
Keywords (in English): 3-homoacylcoumarin, divergent Synthesis, 1,6-addition, cascade reaction, indeno[1,2-c]furan
DOI URL: http://doi.org/10.6345/NTNU201900071
Thesis Type: Academic thesis/ dissertation
Reference times: Clicks: 215  Downloads: 0 
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    • 第一部分為利用本實驗室開發之高醯基香豆素以及 1,3-茚二酮衍生物進
    行連續性反應，並藉由改變其反應條件，希望能控制其反應之化學選擇性來達到多樣性導向合成反應，並建構具有生物活性應用之產物。
    此研究利用高醯基香豆素衍生物與β-酯基芳基亞烯基-1,3-茚二酮衍生物 進行 1,6-加成反應後，因其中間體 dienolate 具有高度活性，可利用控制反應條件來進行 Aldol 或 Michael 之選擇性加成，達到連續性之多樣性導向合成反應，且得到兩種香豆素類似物之骨架。
    第二部分為實驗室先前研究之延伸，利用1,3-茚二酮烯類化合物衍生物與有機膦試劑進行反應，經過重排反應後可得一具有三環結構之呋喃化合物，本研究為優化其反應條件並針對其反應機制進行相關探討。

    Part I : Herein, we demonstrated two vinylogous cascade reactions where in the chemoselectivity is controlled effectively by using two distinct bases resulting in diverse coumarin derivatives. These coumarin derivatives were synthesized through two different cascade reactions viz 1,6-Addition/Aldol addition and 1,6Addition/Michael addition from 3-homoacylcoumarins2 and 2-cinnamylidene-1,3indandiones. By careful optimization of reaction conditions, the selective synthesis of two kinds of coumarin derivatives was achieved successfully in good yields and good diastereoselectivities.
    Part II :
    In 2014 we have developed a organophosphane-mediated reaction to do the βacylation and wittig reaction. Although we got β-acylation product, we didn’t get the wittig reaction product. Instead we’ve got a rearrangement product 8H-indeno[1,2c]furan-8-one. In this research we optimized the standard protocol for the synthesis and study the mechanism for the rearrangement reaction

    摘要.................................................... I Abstract............................................... II 謝志.................................................. III 目錄................................................... IV 縮寫對照表.............................................. VI 第一部分、透過鹼控制高醯基香豆素與 1,3-茚二酮衍生物進行化學選擇性1,6-Addition/Aldol 或 1,6-Addition/Michael 連續反應合成香豆素衍生物............................................... 1 1-1. 前言 ...............................................1 1-1-1. 1,6-麥可加成 ..................................... 2 1-1-2. 串聯反應.......................................... 7 1-1-3. 多樣性導向合成 .................................. 10 1-1-4. 研究動機與起始物架構之應用價值..................... 14 1-2. 實驗結果與討論 .....................................17 1-2-1. 鹼性試劑優化的篩選............................... 17 1-2-2. 溶劑優化的篩選 ................................. 20 1-2-3. 溫度優化的篩選 ................................ 22 1-2-4. 分子篩對反應的影響 .............................. 23 1-2-5.起始物當量數優化篩選............................. 25 1-2-6. 產物 4aa 的添加劑篩選及濃度篩選 .................. 26 1-2-7. 手性催化劑優化及溶劑的篩選 ....................... 27 1-2-8. 取代基效應 ..................................... 30 1-2-9. 反應機制的探討.................................. 33 1-3. 結論及未來展望 .....................................35 1-4. 實驗部分 .......................................... 36 1-4-1. 分析儀器及基本實驗操作 ........................... 36 1-4-2. 反應步驟 ........................................ 38 1-4-3. 起始物實驗數據 .................................. 42 1-4-4. 產物實驗數據 .................................... 47 1-4-5. 光譜探討與解析 .................................. 76 第二部分、透過有機膦試劑、酸酐與亞芳基-1,3-茚二酮合成茚並[1,2-c]呋喃衍生物 ........................................... 77 2-1. 前言 ............................................. 77 2-1-1. 茚並呋喃稠合雜環過去相關報導 ..................... 77 2-1-2. 研究動機 ....................................... 83 2-2. 實驗結果與討論 ................................... 86 2-2-1. 膦試劑優化的篩選 ............................... 86 2-2-2. 溫度優化的篩選 .................................. 87 2-2-3. 鹼性試劑優化的篩選............................... 88 2-2-4. 溶劑優化的篩選 .................................. 89 2-3. 結論及未來展望 .................................... 90 2-4. 實驗部分 .......................................... 91 2-4-1. 分析儀器及基本實驗操作 ........................... 91 2-4-2. 反應步驟 ........................................ 93 2-4-3. 產物實驗數據 .................................... 94 參考文獻 .............................................. 95 附錄一 ................................................. 97 附錄二 ............................................... 214

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