UC San Diego

Cross-coupling strategies have been transformative in the field of complex molecule synthesis providing new ways to construct C-C and C-heteroatom bonds. Transition-metal mediated cross-coupling typically uses nickel or palladium-based precursors to couple

organohalide, or pseudohalide, electrophiles with organometallic nucleophiles.

Recent advancements have expanded cross-coupling partners beyond organohalides to include aldehydes, esters, and amides via C(acyl)-heteroatom bond activation. The work shown in this present thesis, examines the transition-metal mediated decarbonylative cross-coupling method of esters and enolizable carbonyl nucleophiles. Investigations were conducted to examine the electronic, coordinating, and steric effects of substituents of the aryl ester group in order to gain insight into optimal properties for future reaction development. Additionally, a rare example of nucleophilic acyl substitution was observed that is the formal result of acetophenone decomposition into phenol. Mechanistic experiments support this type of mechanism and indicate that this process is not transition-metal-catalyzed.