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研究生： 布巴倫
Ramadoss, Boobalan
論文名稱： 釕和鈷金屬催化醯胺化合物進行碳－氫鍵之炔基化或環化反應之研究
Ruthenium-catalyzed C–H Alkynylation Reaction of Aromatic Amides with Hypervalent Iodine-Alkyne Reagents and Cobalt-Catalyzed Annulation Reactions of Amides with Allenes via C–H Bond Activation
指導教授： 鄭建鴻
Cheng, Chien-Hong
口試委員: 劉瑞雄
Liu, Rai-Shung
蔡易州
Tsai, Yi-Chou
莊士卿
Chuang, Shih-Ching
謝仁傑
Hsieh, Jen-Chieh
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2018
畢業學年度： 106
語文別： 英文
論文頁數： 303
中文關鍵詞： 釕金屬催化反應 、環化反應 、醯胺 、高價碘炔試劑 、炔化反應 、碳氫鍵活化 、鈷金屬催化反應 、丙二烯
外文關鍵詞： Ruthenium-Catalyzed Reaction, Annulation Reactions, Amides, Hypervalent Iodine-Alkyne Reagent, Alkynylation, C-H Activation, Cobalt-Catalyzed Reactions, Allenes
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    • 中文摘要
    本論文主要探討釕金屬與鈷金屬作為催化劑，使用苯并醯胺作為引導基，與高價碘試劑進行鄰位碳－氫鍵活化之炔基化耦合反應，或與丙二烯進行碳－氫鍵活化之環化反應，成功開發新穎之有機合成途徑。

    第一章節中探討探討二價釕金屬催化鄰位碳－氫鍵炔基化反應，使用N-甲氧基苯并醯胺作為引導基，與高價碘試劑1-[(芳基乙炔基]-1,2-苯碘酰-3(1H)-酮進行炔基化反應，合成鄰位炔基化之苯并醯胺化合物。此反應係經由釕金屬進行碳－氫鍵活化、與碘試劑進行氧化加成，再進行還原脫去並得到相對應之產物。

    第二章探討二價鈷金屬催化醯胺化合物與丙二烯之氧化環化反應，合成異喹啉酮與吡啶酮衍生物。此反應利用氨基喹啉作為引導基，經由鈷金屬進行碳－氫鍵活化後，於丙二烯之末端碳進行加成反應，再經由還原脫去與雙鍵異構化生成最終反應產物。

    第三章節則講述三價鈷金屬催化醯胺化合物與丙二烯進行[4+1]環化反應，高效率合成一系列之異吲哚酮衍生物。此反應機構係經由碳－氫鍵活化生成鈷金屬雜環中u間體、丙二烯加成反應、β－氫脫去反應與分子內氫化胺化反應，並得到反應最終產物。三烯中間體的分離與鑑定間接證明了此反應之反應機構。

    ABSTRACT
    In this dissertation, Ru-catalyzed alkynylation and Co-catalyzed annulation reactions have been discussed. For the better understanding, this dissertation has been split into three chapters. Chapter 1 discusses Ru(II)-catalyzed benzamide directed ortho C–H alkynylation reactions with hypervalent iodine reagents, and Chapter 2 demonstrates bidentate-directing group assisted annulation of 8-aminoquinoline amides with allenes under CoII-catalytic conditions to synthesize isoquinolones scaffold. Finally, chapter 3 describes a novel and economical CoIII-catalyzed annulation reaction of benzamides with allenes to make a novel isoindolone structural cores.

    Chapter 1 deals with Ru(II)-catalyzed ortho C–H alkynylation reactions of N-methoxy benzamide with 1-((triisopropylsilyl)ethynyl)-1l3-benzo[d][1,2]iodaoxol-3(1H)-one (TIPS-EBX) as an alkynylating reagent. This reaction commences via Ru-carboxylate assisted C–H cleavage followed by oxidative addition of hypervalent iodine reagent with ruthenacycle, reductive elimination and ligand exchange process to offer the ortho-alkynylated benzamides.

    Chapter 2 elaborates CoII-catalyzed oxidative annulation of amides with allenes. This catalytic reaction proceeds through aminoquinoline‐directed C–H activation followed by the migratory insertion into the terminal carbon of allene, reductive elimination, and eventually, double bond isomerization to give isoquinolin‐1(2H)‐ones and pyridinones in excellent yields.

    Chapter 3 demonstrates an economical Co(III)-catalyzed [4+1] annulation reaction of N-methyl benzamide with allene to afford an isoindolone moiety in good to excellent yields. The novel annulation reaction proceeds via metallacycle formation, allene insertion followed by ꞵ-hydride elimination, and finally, intramolecular 1,2-hydroamination to give the corresponding annulation product in excellent yield with broad substrate scope. Isolation of triene intermediate was achieved that further reveals the plausible mechanism of this reaction.

    TABLE OF CONTENTS Page LIST OF SCHEMES IX LIST OF TABLES X ABBREVIATIONS XIII LIST OF PUBLICATIONS XV CHAPTER 1: Ruthenium-Catalyzed C−H Alkynylation of Aromatic Amides with Hypervalent Iodine−Alkyne Reagents 1 1.1. Introduction 2 1.2. Results and Discussion 14 1.3. Mechanistic Studies 22 1.4. Plausible Mechanism 25 1.5. Summary 26 1.6. Experimental Section 26 1.7. 1H and 13C, NMR, HRMS and IR Data 42 1.8. References 55 CHAPTER 2: Access to Isoquinolin-1(2 H)-ones and Pyridones by Cobalt-Catalyzed Oxidative Annulation of Amides with Allenes. 62 2.1. Introduction 63 2.2. Results and Discussion 74 2.3. Mechanistic Discussion 87 2.5. Proposed Mechanism 88 2.6. Conclusion 89 2.6. Experimental Section 90 2.7. Spectroscopic Data 98 2.8. References 125 CHAPTER 3: Co(III)-Catalyzed [4 + 1] Annulation of Amides with Allenes via C−H Activation. 129 3.1. Introduction 130 3.2. Results and Discussion 144 3.3. Mechanistic Studies 156 3.4. Proposed Mechanism 159 3.5. Conclusion 160 3.6. Experimental Section 161 3.7. Spectroscopic Data 173 3.8. References 192 CRYSTAL STRUCTURES, 1H AND 13C SPECTRA 197

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    Chapter-2

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    Chapter-3

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