Activated Hydrogen Peroxide/Hydroperoxides

Mechanism + Description

The mechanism may vary with the metal and homo/hetero nature of the catalyst. With homogeneous catalysts, several reports have described that O2 generated via the decomposition of H2O2 is not the oxidant. For homogeneous reactions, the active catalyst is probably a peroxy metal species.

 

General comments

The method of activating hydrogen peroxide/hydroperoxides usually on metal catalysts is a variant on the use of air/O2. The reaction can be carried out under mild conditions, but the background decomposition of peroxide or hydroperoxide can lead to higher-than-stoichiometric demands for the oxidant. H2O2 is an attractive oxidant since the by-product is water. Other functional groups may be oxidized.

 

Key references

Dudas, J.; Parkinson, C. J.; Cukan, V.; Chokwe, T. B. Development and Semicommercial Implementation of an Environmentally Benign, Hydrogen Peroxide Mediated Oxidation of Aliphatic Alcohols. Org. Process Res. Dev. 2005, 9 (6), 976-981.

Ni, J.; Yu, W.; He, L.; Sun, H.; Cao, Y.; He, H.; Fan, K. A Green and Efficient Oxidation of Alcohols by Supported Gold Catalysts Using Aqueous H2O2 Under Organic Solvent-Free Conditions. Green Chem. 2009, 11, 756-759.

Santonastaso, M.; Freakley, S. J.; Miedziak, P. J.; Brett, G. L.; Edwards, J. K.; Hutchings, G. J. Oxidation of Benzyl Alcohol Using in Situ Generated Hydrogen Peroxide. Org. Process Res. Dev. 2014, 18 (11), 1455−1460.

Oliveira, R. L.; Kiyohara, P. K.; Rossi, L. M. Clean Preparation of Methyl Esters in One-Step Oxidative Esterification of Primary Alcohols Catalyzedby Supported Gold Nanoparticles. Green Chem. 2009,11, 1366-1370.<

 

Relevant Scale-Up Examples with Scheme

No scale-up examples identified.

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