博碩士論文 109223049 詳細資訊



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姓名 曾宥勲(Yu-Hsun Tseng)  查詢紙本館藏   畢業系所 化學學系
論文名稱 以開環置換聚合反應合成手性共價有機框架材料並將其應用於不對稱催化多烯環化反應之研究
(Synthesis of Chiral Covalent Organic Frameworks via Ring-Opening Metathesis Polymerization and Its Application Study in Asymmetric and Catalytic Polyene Cyclization)
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摘要(中) 大自然中部份天然物為多環化合物，這類化合物擁有良好的生物活性以及藥物開發潛力，因此建構出具有立體選擇性的多環主結構成為化學家追求的目標。

本論文目的在於開發新型手性共價有機框架材料，並應用至不對稱多烯環化反應上。以 R 型 1,1′-聯-2-萘酚之衍生物作為催化單體，並使用格拉布二代試劑將帶有降?烯基的催化單體和架橋分子進行開環置換聚合反應。此法合成的手性共價有機框架材料以碳碳雙鍵鏈接起材料骨架，與四氯化錫進行配位後，形成路易士酸輔助手性布式酸並投入不對稱多烯環化反應上，經不同反應條件篩選後，最終環化產物可超過 40% 的鏡像超越值。
摘要(英) Polycyclic scaffolds are frequently seen in natural products and drugs; therefore, developing synthetic strategies and methods for constructing these scaffolds are essential, especially in an enantioselective way.

In this thesis, we aimed to develop a new chiral covalent organic framework (CCOFs), and apply it to enantioselective polyene cyclization. (R)-Binol with norbornenes on the two arms was used as a monomer and polymerized by using Grubbs second-generation catalyst through ring-opening metathesis polymerization (ROMP) for the formation of CCOF. After treating Tin chloride to generate a Lewis acid-assisted chiral Brønsted acid complex, the activated CCOF was applied to the enantioselective polyene cyclization. Different reaction conditions were then screened to provide, the best result with more than 40% enantiomeric excess.
關鍵字(中) ★ 不對稱多烯環化反應
★ 共價有機框架材料
★ 開環置換聚合反應		 關鍵字(英) ★ asymmetric polyene cyclization
★ Covalent Organic Framework
★ Ring-Opening Metathesis Polymerization
論文目次 中文摘要……………………………………………………………...………….ⅰ
Abstract……………………………………………………………...…………..ⅱ
謝誌…………………………………………………………...……………...…ⅲ
總目錄……………………………………………………………...…………....ⅴ
圖目錄……………………………………………………………..…………..ⅵii
式目錄……………………………………………………………...……………X
表目錄……………………………………………………………...…………..Xii
縮寫說明…………………………………………………………...……...…..Xiⅴ
第一章 緒論……………………………………………..…………...…………1
1-1 多烯環化反應發展介紹…………………………………………………1
1-2 不對稱多烯環化反應之合成策略回顧…………………………………2
1-3 共價有機框架材料………………………………………………..……11
1-4 共價有機框架材料之鍵連方式回顧…………………………..………12
1-5 手性共價有機框架材料……………………………………………..…19
1-6 開環置換聚合反應……………………………………………..………23
1-7 研究動機…………………………………………………………..……26
第二章 結果與討論……………………………………………………...……29
2-1 含有苯乙烯基單體和多烯環化反應起始物之合成………..…………29
2-2 以苯乙烯基聚合之手性有機框架材料合成與應用………………..…35
2-3 以苯乙烯聚合之手性有機框架材料之質譜鑑定…………………..…38
2-4 含有降?烯基單體和架橋分子之合成……………………………..…39
2-5 以降?烯基聚合之手性有機框架材料合成與應用…………..………43
2-6 不對稱多烯環化反應條件篩選………………………………..………46
2-6-1 不同路易士酸之反應測試…………………………………..……46
2-6-2 不同反應溶劑之反應測試……………………………………..…47
2-7 手性有機框架材料合成條件篩選………………………….…………48
2-7-1 不同反應溶劑之反應測試……………………………………..…48
2-7-2 不同反應時間之反應測試………………………………………..50
2-7-3 不同世代格拉布試劑之反應測試……………………………..…51
2-7-4 不同終止試劑之反應測試…………………………………..……53
2-7-5 不同架橋分子之反應測試……………………………………..…54
2-7-6 不同當量架橋分子之反應測試……………………………..……59
2-7-7 不同當量格拉布催化劑之反應測試………………………..……64
2-7-8 以其他方式合成手性有機框架材料並探討其應用…………..…67
2-8 比較單體與手性共價有機框架材料兩者催化功能…….…….……....71
2-9 藉由手性和非手性之 LBA 進行不對稱多烯環化反應…….………72
2-10 以降?烯基聚合之手性有機框架材料性質鑑定……...…………….73
2-11 以手性共價有機框架材料催化不對稱反應之示意圖………………77
第三章 結論…………………………………………………………………...78
第四章 實驗步驟…………………………………………………………...…79
4-1 General Information…………………………………………………..…79
4-2 Synthetic Procedures and Spectra Data………………………….………80
第五章 參考文獻……………………………………………………….……110
附錄…………………………………………………………………...………117
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指導教授 陳榮傑 謝發坤(Rong-Jie Chein Fa-Kuen Shieh) 審核日期 2022-8-16
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