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Author: 郭瑀潔
Kuo, Yu-Chieh
Thesis Title: 一價銠金屬催化芳香基硼酯與降冰片烯衍生物進行不對稱串聯合環反應
Rhodium(I)-Catalyzed Enantioselective Tandem Annulation of Arylboronic Esters with Norbornene Derivatives
Advisor: 吳學亮
Wu, Hsyueh-Liang
Committee: 林民生
Tamio, Hayashi
陳建添
Chen, Chien-Tien
吳學亮
Wu, Hsyueh-Liang
Approval Date: 2022/09/19
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2022
Academic Year: 110
Language: 中文
Number of pages: 239
Keywords (in Chinese): 一價銠金屬催化 、不對稱合環反應 、掌性雙環[2.2.1]雙烯配基 、鏡像選擇性 、掌性茚烷 、芳基硼酯試劑 、降冰片烯衍生物
Keywords (in English): Rhodium(I)-catalyzed, asymmetric tandem annulation, chiral bicyclo[2.2.1]diene ligands, enantioselective, chiral indanes, arylboronic ester, norbornene derivatives
Research Methods: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202201738
Thesis Type: Academic thesis/ dissertation
Reference times: Clicks: 144  Downloads: 7 
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    • 本論文敘述利用一價銠金屬及掌性雙環[2.2.1]雙烯配基L12i所形成之催化劑，催化不同芳基硼酯59與降冰片烯(norbornene)衍生物37進行不對稱合環反應，得到一系列具有茚烷(indane)結構之掌性環化產物60，產率為13–>99%，鏡像超越值為12–99%。此反應的驅動力為環張力能量之釋放，不僅建立了兩個新的碳-碳鍵，也同時生成三個連續的立體中心。此外，本文也探討了具有張力之雙鍵與在烯丙位具有離去基之雙鍵兩者的反應性差異。

    An enantioselective tandem annulation of norbornene derivatives 37 with arylboronic esters 59 is reported. In the presence of 3.0 mol % of Rh(I)-catalyst, which is in situ generated from the [RhCl(C2H4)2]2 and the chiral bicyclo[2.2.1]heptadiene ligand L12i, the desired chiral indanes 60 are obtained in 13–>99% yields with 12–99% ees. This asymmetric transformation, which is triggered by the release of ring strain, not only forms two carbon-carbon bonds, but establishes three consecutive new chiral centers. Furthermore, in this thesis, we also discuss the reactivity difference between the strain olefins and the double bonds with leaving groups at allylic position.

    中文摘要 iii Abstract iv 第一章 緒論 1 第二章 文獻回顧與研究動機 4 2-1環張力釋放之加成反應 4 2-2不對稱烯丙基取代反應 12 2-3串聯合環反應 (Tandem annulation) 15 第三章 配基的設計與合成 18 一、製備本實驗室開發的掌性雙環[2.2.1]雙烯配基L12 19 二、製備本實驗室開發的掌性雙環[2.2.1]雙烯配基L13 20 第四章 實驗結果與討論 22 4-1溶劑效應 24 4-2 添加劑效應 26 4-3 溫度效應 27 4-4 配基效應 29 4-5催化量效應 31 4-6 最佳反應條件 32 4-7 不同芳基硼酯作為親核試劑之反應性探討 33 4-8 具有不同保護基的降冰片烯衍生物37之反應性探討 36 4-9.1 不同結構的降冰片烯衍生物37之反應性探討(一) 38 4-9.2 不同結構的降冰片烯衍生物37之反應性探討(二) 41 4-10 以β位具有甲基取代之芳基硼酯63作為親核試劑之反應性探討 43 4-11 一般雙鍵化合物之反應性探討 45 第五章 立體組態與反應機制探討 47 5-1 絕對立體組態探討 47 5-2 反應機構探討 48 5-3 控制實驗 51 第六章 結論 52 第七章 實驗部分 53 第八章 參考文獻 129 附錄一 X-ray 單晶數據與ORTEP解析圖譜 132 附錄二 核磁共振光譜 148 附錄三 其他 237

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