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New Applications of Arynes in Organic Synthesis
Dissertation

New Applications of Arynes in Organic Synthesis

Thiruvellore Thatai Jayanth
Doctor of Philosophy (PHD), 國立清華大學, 化學系
2006

Abstract

aryne benzyne palladium nickel ene-reaction three-component coupling
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.

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