UC San Diego

Transition metal-catalyzed cross-coupling is a powerful methodology to strategically form carbon-carbon or carbon-heteroatom bonds. Advancements in cross-coupling strategies with diverse organometallic nucleophile reagents have been well recognized, however, developments that expand the scope of viable electrophilic partners have only recently been invigorated. Of particular interest is the development of new coupling strategies where both the nucleophilic and electrophilic coupling partner could be derived from oxygenated precursors rather than halogenated precursors, which is the current standard. This thesis describes efforts toward the development of new synthetic methodologies to achieve a-vinylation of enolizable carbonyls in two parts: 1) Pd-catalyzed decarbonylative Hiyama-type cross-coupling of cinnamate esters and aryl silanes and 2) radical-mediated oxidative decarboxylative coupling of cinnamic acids and simple ketones.