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研究生： 林冠宇
Lin, Kuan-Yu
論文名稱： 利用一價銠金屬催化α-重氮-β,γ-不飽和酯類化合物與苯胺化合物進行不對稱加成反應 : 合成γ-胺基α,β-不飽和酯類化合物與八氫吲哚衍生物
Highly Enantioselective and Regioselective Rh (I)-Catalyzed Addition of Anilines to α-Diazo-β,γ-unsaturated esters:Synthesis of Chiral γ-Amino α,β-unsaturated Esters and An Octahydroindole Derivative
指導教授： 吳學亮
Wu, Hsyueh-Liang
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2020
畢業學年度： 108
語文別： 中文
論文頁數： 331
中文關鍵詞： 一價銠金屬 、銠金屬碳烯 、重氮酯類 、掌性雙環[2.2.2]雙烯配基
英文關鍵詞： rhodium (I)-catalyzed, rhodium carbenoid, chiral bicyclo [2.2.2] octadiene ligand, α-diazo β,γ-unsaturated esters
DOI URL： http://doi.org/10.6345/NTNU202000866
論文種類： 學術論文
相關次數： 點閱：178  下載：0 
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    • 本篇論文論述利用一價銠金屬與掌性雙環[2.2.2]雙烯配基L3d形成錯合物，催化α-重氮-β,γ-不飽和酯類化合物11，反應形成銠金屬碳烯(rhodium carbenoid)中間體，與苯胺化合物12進行不對稱加成反應，成功地合成出一系列具有掌性中心之主要產物γ-胺基α,β-不飽和酯類化合物13，產率為6–85%，鏡像超越值為22–>99.5%，及副產物為具有掌性中心之α胺基β,γ-不飽和酯類化合物14，產率為15–54%，鏡像超越值為15–90%。將具有掌性的γ胺基α,β-不飽和乙酯化合物13al經由數步反應步驟，可合成出八氫吲哚衍生物99。

    An unprecedented rhodium (I)-catalyzed asymmetric N−H insertion reaction of α-diazo β,γ-unsaturated esters with available anilines 12 was reported. The asymmetric reaction permitted an efficient synthesis of chiral γ-amino α,β-unsaturated esters 13, in the presence of a Rh-catalyst in situ generated from [RhCl(C2H4)2]2 and chiral bicyclo [2.2.2] octadiene ligand L3d, with excellent enantioselectivities (22–>99.5% ees) and in good yields (6–85%) under mild conditions, along with α-amino β, γ-unsaturated esters 14 in 15–54% yields and with 15–90% ees. The method was applied in the synthesis of a bioactive octahydroindole derivative 99 .

    中文摘要 i Abstract ii 謝誌 iii 目錄 iv 圖目錄 vi 表目錄 viii 縮寫對照表 ix 第一章 緒論 1 第二章 文獻回顧 5 第三章 實驗設計與概念 14 3-1 掌性雙烯配基62之開發 14 3-2 製備本實驗室開發之掌性雙環[2.2.1]雙烯配基L1 15 3-3 製備本實驗室開發之含醯胺類掌性雙環[2.2.1]雙烯配基L2 16 3-4 製備掌性雙環醯胺類[2.2.2]雙烯配基L3 17 3-5 製備α-重氮-β,γ-不飽和酯類化合物11 18 3-6 製備α-重氮-β,γ-不飽和乙酯化合物88 19 第四章 實驗結果與討論 20 4-1 探討親核試劑之效應 20 4-2 探討溫度之效應 25 4-3 探討配基之效應I 27 4-4 探討配基之效應II 28 4-5 探討配基之效應III 29 4-6 探討配基之效應IV 30 4-7 探討溶劑之效應 31 4-8 探討反應滴加時間之效應 32 4-9 親核試劑效應之探討I 33 4-10 親核試劑效應之探討II 35 4-11 親核試劑效應之探討III 37 4-12 親核試劑效應之探討IV 39 4-13 親核試劑效應之探討V 41 4-14 動力學拆析效應之探討 42 4-15 動力學同位素效應之探討 45 4-16 絕對立體化學之探討 47 4-17 反應機構之探討 48 第五章 合成應用 49 第六章 結論 52 第七章 實驗部分 53 參考文獻 126 附錄一 X-ray單晶數據與ORTEP解析圖譜 130 附錄二 核磁共振光譜圖 183

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