Mon, Nov. 13, 2017, 4:30pm
Edward C. Taylor Auditorium, Frick B02
Host: Robert Knowles
Kinetic isotope effects in organocatalysis and transition-metal catalysis
Our research program utilizes experimental and theoretical 13C kinetic isotope effects (KIEs) to investigate mechanisms of catalytic reactions. In the area of asymmetric organocatalysis, this approach is utilized to identify new mechanistic pathways and uncover fine details of complex catalytic cycles. These studies provide the basis for the rational design of novel concepts in asymmetric catalysis. Our more recent efforts address challenging mechanistic questions in the area of transition-metal catalysis. 13C KIEs are a sensitive probe of the electronics, oxidation state, and chemistry occurring at the metal center at the transition state of the rate-determining step.
This seminar will provide an overview of our research program and present unpublished results from (a) a mechanistic study of an organocatalytic asymmetric epoxidation reaction, (b) an investigation of the transmetalation step of the Suzuki-Miyaura reaction, and (c) the development of a novel mechanistic probe for the rapid determination of 13C KIEs using ‘designed’ starting materials.
 Ashley, M. A.; Hirschi, J. S.; Izzo, J. A.; Vetticatt, M. J. J. Am. Chem. Soc. 2016, 138, 1756-1759.
 (a) Bandar J. S.; Sauer, G. S.; Wulff, W. D.; Lambert, T. H.; Vetticatt, M. J. J. Am. Chem. Soc. 2014, 136, 10700-10707.
(b) Gang, H.; Gupta, A.; Huang, L.; Zhao, W.; Xiaopeng, Y.; Osminski, W.; Huang, R.; Wulff, W. D.; Izzo, J. A.; Vetticatt, M. J. J. Am. Chem. Soc. 2017, 139, 10267-10285.
 Macharia J.; Victor, W.; Hong, Y.; Harris, L.; Hirschi, J. S.; Evans, G. B.; Vetticatt, M. J. Angew. Chem. Int. Ed. 2017, 56, 8756-8760.