Date of Award
Doctor of Philosophy (PhD)
Patrick J. Walsh
PART I: Chemists are relentlessly searching for innovative approaches to activate the least reactive bonds and harnessing the newly found reactivity to develop novel methods. Therefore, C–F bonds, the strongest carbon heteroatom single bond, have garnered widespread attention as challenging and attractive targets. We proposed that heterobimetallic Pd/Mg catalysts can exhibit cooperativity to facilitate the activation of aryl fluorides and achieved the wild application of this catalyst system in this work. Next, the reaction partner was extended to pronucleophiles, wherein weakly acidic C(sp3)−H bonds are deprotonated to reveal the nucleophilic coupling partner. N-Heterocyclic carbene (NHC) ligand with Nickel was found to be crucial to mediate C−F bond activations. And this new method was proved to enable the synthesis of a wide range of triarylmethane derivatives.
PART II: Chiral sulfoxides are prevalent in natural products, bioactive compounds, and marketed therapeutics. They have also been employed as chiral auxiliaries in a range of reaction classes, and more recently have attracted attention as chiral ligands. We demonstrated a palladium-catalyzed coupling of both aryl and alkyl sulfenate anions with vinyl/aryl bromides to afford a variety of enantioenriched sulfoxides under very mild condition in one step.
Wu, Chen, "Part I: C-F Bond Activation Via Different Catalysts Part Ii: Enantioselective Synthesis Of Sulfoxides From Sulfenate Anions" (2019). Publicly Accessible Penn Dissertations. 3412.