Mechanistic Guidance Leads to Enhanced Site-Selectivity in C–H Oxidation Reactions Catalyzed by Ruthenium bis(Bipyridine) Complexes
Jeremy Griffin, David B. Vogt, J. Du Bois, Matthew S. Sigman
Abstract
The development of an operationally simple C–H oxidation protocol using an acid-stable, bis(bipyridine)Ru catalyst is described. Electronic differences remote to the site of C–H functionalization are found to affect product selectivity. Site-selectivity is further influenced by the choice of reaction solvent, with highest levels of 2° methylene oxidation favored in aqueous dichloroacetic acid. A statistical model is detailed that correlates product selectivity outcomes with computational parameters describing the relative “electron-richness” of C–H bonds.
Topics & Concepts
RutheniumCatalysisSelectivityChemistryBipyridinePhotochemistryCombinatorial chemistryOrganic chemistryCrystal structureCatalytic C–H Functionalization MethodsOxidative Organic Chemistry ReactionsAsymmetric Hydrogenation and Catalysis