Abstract:

We have developed a set of new transition metal-catalyzed C-H functionalization methodologies employing various tether strategies. These methods feature: (a) use of silyl group as a tether between a substrate and a reagent, thus transforming intermolecular reaction into an intramolecular reaction; (b) employment of a silicon-tethered directing group, which is traceless or easily convertible into valuable functionalities; (c) use of reactive silyl-tethered hydrosilane group; and (d) introduction of new N/Si-chelation concept that allows for a remote activation of aliphatic C-H bonds. We uncovered new reactivity of hybrid Pd-radical species, generated at room temperature under visible light without use of exogenous photosensitizers. This led to the development of novel transformations, including new types of Heck reaction, aliphatic C–H functionalization methods, as well as new cascade transformations. A set of both directed and direct functionalization methods have been developed. The scope of these transformations will be demonstrated and the mechanisms will be discussed.

Bio:

Vladimir Gevorgyan received his PhD from the Latvian Institute of Organic Synthesis in 1984. After two years of Postdoctoral research (1992-1994, JSPS- and Ciba-Geigy International Postdoctoral Fellowships) at Tohoku University, Japan, and a visiting professorship (1995) at CNR, Bologna, Italy, he joined faculty at Tohoku University (Assistant Professor, 1996; Associate Professor, 1997-1999). Vladimir Gevorgyan joined UIC as an Associate Professor in 1999. He was promoted to the rank of Full Professor in 2003, and a Distinguished Professor of Liberal Arts and Sciences in 2012. In 2019, Vladimir Gevorgyan moved to Texas to become a Robert A. Welch Distinguished Chair in Chemistry at the University of Texas at Dallas. He also holds a Professor position at the University of Texas Southwestern Medical Center.

Gevorgyan group has been working in development of regio- and chemoselective transition metal-catalyzed annulation reactions and their application in the synthesis of multifunctional, polysubstituted aromatic compounds; development of novel transition metal-catalyzed methodologies for synthesis of strained molecules and heterocyclic compounds; development of novel direct and directed C-H functionalization methods; and development of robust methodologies amendable for synthesis of small molecules libraries for wide biological screening. Lately, the group focuses on development of photoexcited chemistry of transition metals. In all projects, the emphasis is placed on conceptual novelty and potential application of the newly developed methods.