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.