Herein, we report the ruthenium-catalyzed ortho C–H alkenylation of a wide range of N-aryloxazolidinone scaffolds. Alkenylation was achieved with complete monoselectivity with a scope of 27 examples in 2-MeTHF. Yields ranged from 23 to 94%, producing highly decorated oxazolidinone scaffolds. A kinetically relevant C–H cleavage was also observed with a kinetic isotope effect (KIE) of ∼2. Density functional theory calculations provided information about mechanism, detailing the β-hydride elimination as the most energetically challenging step of 13.5 kcal mol–1. In-depth computational kinetic studies also predicted a KIE of 2.17 for C–H cleavage and an intrinsic KIE for the reaction of 2.22, in line with the experimentally observed value.
Leitch, J. A., Wilson, P. B., McMullin, C. L., Mahon, M. F., Bhonoah, Y., Williams, I. H., & Frost, C. G. (2016). Ruthenium(II)-Catalyzed C–H Functionalization Using the Oxazolidinone Heterocycle as a Weakly Coordinating Directing Group: Experimental and Computational Insights. ACS Catalysis, 6(8), 5520-5529. https://doi.org/10.1021/acscatal.6b01370