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研究生： 迦恩
Thiruvellore Thatai Jayanth
論文名稱： 苯炔化合物在有機合成上的新應用
New Applications of Arynes in Organic Synthesis
指導教授： 鄭建鴻
Chien-Hong Cheng
口試委員:
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： 2007
畢業學年度： 95
語文別： 英文
論文頁數： 251
中文關鍵詞： aryne 、benzyne 、palladium 、nickel 、ene-reaction 、three-component coupling
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    • ABSTRACT

    Arynes are a truly amazing species which has found wide applications in organic chemistry despite the fact that it has to be generated in situ. Particularly, the introduction of 2-(trimethylsilyl)phenyl triflate as an aryne precursor that operates under mild reaction conditions has enabled the development of a variety of reactions which also includes transition-metal mediated aryne carbon-carbon bond forming processes. This thesis describes five new reactions that focus on the application of arynes in organic synthesis employing o-silyl aryltriflates as aryne precursors. The first three chapters describes palladium-catalyzed carbopalladation reactions involving arynes with each chapter dealing with a facet of palladium chemistry viz., [2 + 2 + 2] cyclotrimerization, three-component coupling and C-H activation. The fourth chapter involves a novel nickel-catalyzed coupling involving arynes. The final chapter deals with the ene reaction of arynes with alkynes.
    □Chapter 1 is devoted to give a small introduction as well as a brief review of aryne chemistry over the past 100 years. However, the second half of the chapter 1 reviews almost all the reports that have appeared involving o-silyl aryltriflates as aryne precursors.
    □Chapter 2 describes a [2+2+2] cocyclotrimerization of arynes with bicyclic alkenes leading to polyaromatic hydrocarbons.
    Chapter 3 deals about a palladium-catalyzed three-component coupling of arynes, allylhalides and arylorganometallic reagents.
    Chapter 4 illustrates a palladium-catalyzed annulation reaction of arynes with aryl halides leading to functionalized triphenylenes.
    Chapter 5 explains a nickel-catalyzed three-component coupling involving arynes, enones and organoboronic acids.
    Chapter 6 is about the ene reaction of arynes with alkynes.

    TABLE OF CONTENTS ACKNOWLEDGEMENT I ABSTRACT III LIST OF SCHEMES V LIST OF TABLES VII ABBREIVATIONS VIII LIST OF MAJOR PUBLICATIONS IX CHAPTER 1 - Introduction to Aryne Chemistry 1 1.1 – Introduction 2 1.2 - A Brief History of Arynes 2 1.3 -Physical organic chemistry of arynes 3 1.3.1- para-Arynes and Bergman Cyclization: 4 1.4 -Generation Methods of Arynes in Organic Chemistry 5 1.4.1 -Generation of arynes from ortho-silyl aryltriflates 6 1.5 -Application of Arynes in organic synthesis 7 1.5.1 -Use of arynes in organic synthesis (generation from earlier methods) 7 1.5.1a -Pericylic Reactions of Arynes: 7 1.5.1b -Nucleophilic Addition to Arynes: 10 1.5.2 -Use of arynes generated from ortho-silyl aryltriflates (20) in organic synthesis: 14 1.5.2a -Organic reactions employing ortho-silyl arytriflates: 14 1.5.2b -Transition-Metal Catalyzed Reactions employing ortho-silyl arytriflates: 20 1.6 -Conclusion: 25 1.7 -References: 26 CHAPTER 2 - Palladium-Catalyzed Cocyclotrimerization of Arynes with Bicyclic Alkenes. 33 2.1 Introduction 34 2.2 Results and Discussion 37 2.3 Mechanistic Discussion 42 2.4 Synthesis of Benzo[b]triphenylenes 43 2.5 Retro Diels-Alder Reaction 45 2.6 Conclusion 46 2.7 Experimental Section 46 2.8 Spectroscopic Data 50 2.9 References: 59 CHAPTER 3 - Palladium-Catalyzed Three-Component Coupling of Arynes, Allylic Halides, and Arylorganometalic Reagents. 65 3.1 Introduction 66 3.2 Results and Discussion: 68 3.3 Mechanistic Discussion: 75 3.4 Conclusion: 77 3.5 Experimental Section: 78 3.6 Spectroscopic Data: 79 3.7 References: 86 CHAPTER 4 - Palladium-Catalyzed Annulation of Arynes with Aryl Halides. 91 4.1 Introduction 92 4.2 Results and Discussion: 96 4.3 Mechanistic Discussion: 102 4.4 Conclusion: 104 4.5 Experimental Section: 104 4.6 Spectroscopic Data: 105 4.7 References: 109 CHAPTER 5 - Nickel-Catalyzed Three-Component Coupling of Arynes, Alkenes and Organoboronic Acids 113 5.1 Introduction 114 5.2 Results and Discussion: 115 5.3 Mechanistic Discussion: 121 5.4 Conclusion: 123 5.5 Experimental Section: 123 5.6 Spectroscopic Data: 125 5.7 References: 133 CHAPTER 6 - Ene Reaction of Arynes with Alkynes 137 6.1 Introduction 138 6.2 Results and Discussion: 141 6.3 Conclusion: 146 6.4 Experimental Section: 146 6.5 Spectroscopic Data: 148 6.6 References: 155 CHAPTER 2 – Copies of 1H NMR and 13C NMR spectra 160 CHAPTER 3 – Copies of 1H NMR and 13C NMR spectra 180 CHAPTER 4 – Copies of 1H NMR and 13C NMR spectra 194 CHAPTER 5 – Copies of 1H NMR and 13C NMR spectra 210 CHAPTER 6 – Copies of 1H NMR and 13C NMR spectra 230

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