Methodological studies of α-halogenated carbonyls and the synthetic investigation of dihydroresorcylide

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The research presented herein consisted of projects with focuses on metal enolates and silane chemistry, and their uses in methodology and total synthesis. The projects were divided into three distinct chapters. The first chapter covers the development of highly functionalized pyran motifs that are commonly found in classes of natural products such as Bryostatins via an intramolecular Heck reaction with a novel palladium enolate transfer. A bromoethoxy pentanoate compound was synthesized through several steps and was then subjected to catalytic reactions with conditions found in literature where many variations were changed in attempts to obtain the desired six-membered ring. The second chapter consists of the total synthesis of Dihydroresorcylide via a novel palladium enolate ring closure. This structure has been synthesized twice before, however both syntheses undergo a ring closing metathesis to create the macrocycle. The macrocyclization attempts were based on literature published by Buchwald and Hartwig. The third project studies the halogenation of a trialkylsilyl bond through what is believed to be a bromonium ion intermediate followed by an SN2 like elimination according to work published by Tamao and company. Majority of the halogenations proceeded in good yields and with complete inversion of stereochemistry.

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Organic chemistry