Mechanistic Guidance Leads to Enhanced Site-Selectivity in C–H Oxidation Reactions Catalyzed by Ruthenium bis(Bipyridine) Complexes

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.