01/17/19 - 9:45 AM to 11:00 AM
Department Seminar: C. Rose Kennedy, Ph.D.
Leveraging Mechanistic Insight to Enable Catalyst-Controlled Chemo-, Regio- & Stereoselective C–C Bond Formation
Mechanistic elucidation provides potent tools for enabling the design of efficient and selective catalytic transformations. Examples of mechanism-guided method development, drawing from the complementary strengths of ion-pairing organocatalysis and organometallic chemistry to achieve selective C–C bond formation, are described.
In the former case, combined experimental and computational analyses delineating the mechanisms of representative amido-thiourea-catalyzed transformations are discussed. Insights from these studies enabled (i) the rational design of linked bis-thioureas that impart enhanced efficiency for enantioselective anion-abstraction catalysis and (ii) the introduction of a synergistic ion-binding strategy for asymmetric catalysis of transformations involving electronically diffuse transition structures.
In the latter case, iron complexes bearing redox-active ligands are explored as catalysts for hydrovinylation and cycloaddition reactions proceeding through the intermediacy of metallacycles. Mechanistically informed ligand designs were leveraged to control metallacycle formation and fate to upgrade olefinic coupling partners with control of chemo-, regio-, and diastereoselectivity. Applications of the resulting cycloadducts for the synthesis of fuels, polymers, and fine chemicals are discussed.
C. Rose Kennedy
C. Rose Kennedy, Ph.D., is a National Institutes of Health post-doctoral fellow in the Department of Chemistry at Princeton University, working with Professor Paul Chirik. She earned her doctorate from Harvard University, and her bachelor's from the University of Rochester.
Rose's long-term research interests lie in the development of sustainable chemo-, regio-, and stereoselective catalytic methods for valorization of chemical feedstock (ranging from petrochemical waste to biomass) to produce useful synthetic building blocks and materials for applications in fine chemical synthesis (pharma, flavors, fragrances, agrochemicals, etc.) and energy storage. Strategies to achieve these goals will draw from the complementary strengths of organometallic chemistry and organocatalysis. Particular emphasis will be placed on rational manipulation of attractive secondary coordination sphere interactions to achieve precise control over competing reaction pathways. This work will rely heavily on catalyst design driven by insights gleaned from mechanistic elucidation. These pursuits lie at the interface of synthetic organic and organometallic chemistry, and they draw from state-of-the-art experimental and computational techniques in physical organic and inorganic chemistry.
Event DetailsLocation: 331 Smith HallHost: Professor Ian TonksSpeakers:
- C. Rose Kennedy, Ph.D.
- Department of Chemistry
- Princeton University