Mathew Vetticatt

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^[1] and uncover fine details of complex catalytic cycles.^[2] These studies provide the basis for the rational design of novel concepts in asymmetric catalysis.^[3] 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This seminar will provide an overview of our research program and present unpublished results from (a) a mechanistic study of an organocatalytic asymmetric epoxidation reaction, (b) an investigation of the transmetalation step of the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. 

^[1] Ashley, M. A.; Hirschi, J. S.; Izzo, J. A.; Vetticatt, M. J. J. Am. Chem. Soc. 2016, 138, 1756-1759.

^[2] (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.

^[3] 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.