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Oxidation via low-energy electron transfer. Development of green oxidation methodology via a biomimetic approach (OXLEET)
Date du début: 1 janv. 2010, Date de fin: 31 déc. 2015 PROJET  TERMINÉ 

Oxidation reactions are of fundamental importance in Nature and are key transformation in organic synthesis. There is currently a need from society to replace waste-producing expensive oxidants by environmentally benign oxidants in industrial oxidation reactions. The aim with the proposed research is to develop novel green oxidation methodology that also involves hydrogen transfer reactions. In the oxidation reactions the goal is to use molecular oxygen (air) or hydrogen peroxide as the oxidants. In the present project new catalytic oxidations via low-energy electron transfer will be developed. The catalytic reactions obtained can be used for racemization of alcohols and amines and for oxygen- and hydrogen peroxide-driven oxidations of various substrates. Examples of some reactions that will be studied are oxidative palladium-catalyzed C-C bond formation and metal-catalyzed C-H oxidation including dehydrogenation reactions with iron and ruthenium. Coupled catalytic systems where electron transfer mediators (ETMs) facilitate electron transfer from the reduced catalyst to molecular oxygen (hydrogen peroxide) will be studied. Highly efficient reoxidation systems will be designed by covalently linking two electron transfer mediators (ETMs). The intramolecular electron transfer in these hybrid ETM catalysts will significantly increase the rate of oxidation reactions. The research will lead to development of more efficient reoxidation systems based on molecular oxygen and hydrogen peroxide, as well as more versatile racemization catalysts for alcohols and amines.

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