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.
Controlling Selectivity in Aliphatic C−H Oxidation through Supramolecular Recognition / Vidal, D.; Olivo, G.; Costas, M.. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 24:20(2018), pp. 5042-5054. [10.1002/chem.201704852]
Controlling Selectivity in Aliphatic C−H Oxidation through Supramolecular Recognition
Olivo G.
;
2018
Abstract
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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.