Controlling Selectivity in Aliphatic C−H Oxidation through Supramolecular Recognition

Aliphatic C−H oxidation is the most straightforward approach to functionalize hydrocarbon skeletons. The main challenge of this reaction is the control of site selectivity, given the multiple C−H bonds present in any organic molecule. Natural enzymes elegantly solve this problem through the interplay of different interactions that geometrically orient the substrate to expose a single C−H bond to the active unit, thus overriding intrinsic reactivity patterns. A combination of molecular catalysts and supramolecular receptors can be a promising way to replicate such control. This strategy indeed unlocks hydroxylation of C−H bonds that are not accessible with conventional methodologies, in which the selectivity is dictated by the geometry of the substrate–receptor adduct. Herein, we review the reports of recognition‐driven C−H oxidation reactions and highlight the key design principles that inspired these works.