Catalyst-Controlled Aliphatic C–H Oxidations with a Predictive Model for Site-Selectivity

Selective aliphatic
C-H bond oxidations may have a profound impact
on synthesis because these bonds exist across all classes of organic
molecules. Central to this goal are catalysts with broad substrate
scope (small-molecule-like) that predictably enhance or overturn the
substrate’s inherent reactivity preference for oxidation (enzyme-like).
We report a simple small-molecule, non-heme iron catalyst that achieves
predictable catalyst-controlled site-selectivity in preparative yields
over a range of topologically diverse substrates. A catalyst reactivity
model quantitatively correlates the innate physical properties of
the substrate to the site-selectivities observed as a function of
the catalyst.