Allenylsilane Synthesis and Reactivity of Them (Part I) and Group 11 Metal-Catalyzed Reactions (Part II)
thesisposted on 21.06.2016 by Nam-Kyu Lee
In order to distinguish essays and pre-prints from academic theses, we have a separate category. These are often much longer text based documents than a paper.
This thesis has two mainparts. Part I is composed oftwo chapterswhich describe new and convenient method for allenylsilane synthesis and formal ene-type reaction of silylallenes with triplet oxygen. Part II consists of two chapters describing Au- and Ag-catalyzed cascade reactionsinvolving cyclization and trapping of the resulting oxocarbenium intermediates with weaknucleophiles, and hydroarylation of arynes catalyzed by silver for biaryl synthesis Specifically, in chapterone, synthetic methods for allenesand reactions of allenylsilanes are briefly reviewed in introduction. Reaction scope for allenylsilane synthesis from ketones and its mechanism are discussed.In chapter two,a brief summary ofene reaction, especially singlet oxygen ene reaction, is presented.The generality forautooxidation of silylallenes and its mechanistic study are discussed. In chapter three, a brief survey for Au- and Ag-catalyzed cyclization reactions and trapping of oxocarbenium intermediate is provided.The reaction scope of cascade reaction involving Au- and Ag-catalyzed cyclizationof alkynol and phosphonation and allylation of resulting oxocarbenium intermediate is discussed. Finally, in chapter four, methods for constructing biaryls were briefly reviewed and the reactivity of arynestoward arenes is provided in introduction. The development of inter- and intramolecular hydroarylation or arynes with a Ag catalyst and its reaction mechanism are discussed.