Environmentally friendly chemoselective oxidation of primary aliphatic amines by using a biomimetic electrocatalytic system.
Environmentally friendly oxidation of primary aliphatic amines to imines has been successfully achieved, under metal-free conditions, by the use of diverse electrogenerated o-azaquinone mediators. High catalytic performance, together with high chemoselectivity, were observed with electron-poor o-azaquinone catalysts generated from 2-aminoresorcinol derivatives. Similar to copper amine oxidase enzymes, these mediators exhibited lower reactivity toward alpha-branched primary amines and no reactivity toward secondary amines. In the case of 3,4-aminophenol derivatives lacking a 2-hydroxy group, the generated o-azaquinone species failed to catalyze the oxidation of the amine to the corresponding imine. Further mechanistic considerations allowed a rationalization of the crucial role of the 2-hydroxy group in converting a catalytically inert species into a highly effective biomimetic catalyst.
Largeron
Martine
M
UMR 8638 CNRS-Université Paris Descartes, Faculté des Sciences Pharmaceutiques et Biologiques, 4, avenue de L'Observatoire, 75270 Paris Cedex 06, France. martine.largeron@uni-paris5.fr
Chiaroni
Angèle
A
Fleury
Maurice-Bernard
MB
D006631:Amine Oxidase (Copper-Containing) / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D040761:Biomimetic Materials / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D006860:Hydrogen Bonding; D007097:Imines / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011809:Quinones / Q000737:chemistry*
D000588:Amines; D007097:Imines; D011809:Quinones; C527935:o-azaquinone; D006631:Amine Oxidase (Copper-Containing)