Rhodium-catalyzed intramolecular carboacylation of alkenes, achieved using quinolinyl ketones containing tethered alkenes, proceeds via the activation and functionalization of a carbon–carbon single bond. This transformation has been demonstrated using RhCl(PPh3)3 and [Rh(C2H4)2Cl]2 catalysts. Mechanistic investigations of these systems, including determination of the rate law and kinetic isotope effects, were utilized to identify a change in mechanism with substrate. With each catalyst, the transformation occurs via rate-limiting carbon–carbon bond activation for species with minimal alkene substitution, but alkene insertion becomes rate-limiting for more sterically encumbered substrates. Hammett studies and analysis of a series of substituted analogues provide additional insight into the nature of these turnover-limiting elementary steps of catalysis and the relative energies of the carbon–carbon bond activation and alkene insertion steps.
Repository citation: Lutz, J. Patrick; Rathbun, Colin M.; Stevenson, Susan M.; Powell, Breanna M.; Boman, Timothy S.; Baxter, Casey E.; Zona, John M.; and Johnson, Jeffrey B., "Rate-Limiting Step of the Rh-Catalyzed Carboacylation of Alkenes: C–C Bond Activation or Migratory Insertion?" (2012). Faculty Publications. Paper 356.
Published in: Journal of the American Chemical Society, Volume 134, Issue 1, January 11, 2012, pages 715-722. Copyright © 2012 American Chemical Society, Washington, DC.