Carbon-carbon single bonds form the framework for many organic molecules, but in most cases, they cannot be functionalized.  This presentation will summarize the mechanistic investigation of the rhodium-catalyzed intramolecular carboacylation of an alkene, proposed to proceed through carbon-carbon bond activation. A kinetic analysis revealed an unusual first order rate law with no rate dependence upon substrate. Additional experiments identified the catalytic resting state, while determining activation parameters and 12C/13C kinetic isotope effects. Further studies indicate that electron-donating groups increase the rate of reaction. This conclusion is consistent with the kinetics of the parent compound, as electron-donating substituents would be expected to stabilize the high-energy, electron-deficient intermediate of the rate-limiting C-C insertion step.  A related mechanistic investigation with a second rhodium catalyst has revealed a similar but distinct mechanism.  The combined insight from these studies promises to guide the development of new carbon-carbon single bond activation methodologies.

Mechanistic investigations of alkene carboacylation via C-C bond activation in quinolinyl ketones

243rd National Meeting (2012)

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