Transition metals can catalyze the functionalization of classically inert C–H bonds, enabling the evolution of more efficient synthetic strategies. Because C–H bonds are ubiquitous in organic molecules, differentiating between possible sites for C–H functionalization remains a key challenge. One strategy for controlling site selectivity involves the use of a directing group that can coordinate to the metal catalyst (ligand-directed C–H functionalization). My PhD and postdoctoral research has centered on the development of mild and selective ligand-directed C–H functionalization methodology, as well as understanding the factors influencing site selectivity when more than one C–H bond is accessible to the catalyst. In the Sanford lab at the University of Michigan, I focused on high-valent Pd-catalysis for C–H functionalization. There, we developed a C–H arylation reaction that merges Pd- with photoredox catalysis, rerouting the reaction mechanism through a radical pathway and enabling arylation to take place under mild conditions. Additionally, we developed a mild C–H alkylation reaction in conjunction with Mn(III) oxidants, and designed a transformable directing group for C–H functionalization. In the Houk lab at UCLA, I have examined the origin of the observed high site selectivity of pyridine N-oxide substrates in a Rh(III)-catalyzed ligand-directed C–H functionalization reaction. In this reaction, two C–H bonds are accessible to the metal. My calculations show that two key mechanistic steps are both highly selective for reaction at the C(2) position of pyridine N-oxide substrates, and this selectivity arises from factors that include favorable catalyst-substrate electrostatic interactions in the transition states. In the future, I will combine my experimental and theoretical training to design and develop new catalytic systems for addressing current global challenges, with a particular focus on sustainable energy and materials.

Experimental and theoretical studies: Selective metal-catalyzed C–H functionalization

250th National Meeting (2015)

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