Palladium-Catalyzed Cross-Coupling and Related Reactions of Non-Classical Electrophiles Focusing on Esters

This thesis summarizes work related to the development of mild palladium-catalyzed cross- coupling reactions of phenyl- and benzyl- esters, which undergo different C-O bond cleavage selectivity, the scope of the reactions and applications, and mechanistic understanding of precatalyst activation and the oxidative addition steps. The first chapter of this thesis is an introduction summarizing palladium-catalyzed cross-coupling reactions of non-classical electrophiles. The second chapter focus on the development of mild palladium-catalyzed non- decarbonylative Suzuk-Miyuara and Buchwald Hartwig cross-coupling reactions of phenyl aryl- and alkyl-esters to generate ketenes and amides, respectively. The third chapter is the extension of the Suzuki-Miyuara reactions to phenyl ester derivatives of aspartic acid to synthesize aryl amino ketones. Chapter four describes the development of mild palladium-catalyzed Suzuki-Miyuara reactions of diaryl methyl 2,3,4,5,6-pentafluorobenzoates to synthesize triarylmethanes.The first appendix describes preliminary work on palladium-catalyzed benzylic decarboxylation reactions as a more atom economical method for the synthesis of diarylmethanes. The second appendix describes preliminary work on palladium-catalyzed Suzuki-Miyaura reactions of activated aziridines and stoichiometric reactions of phosphine ligated nickel complexes with activated aziridines