Reactivity of Hydrogen Peroxide, Alkyl Hydroperoxides, and Peracids

To activate O2 to be a more effective oxidant reduce it to HOOH 

The reactivity of hydroperoxides is primarily dependent upon their unique bond energies (e.g., H-OOH, 90 kcal HO-OH, 51 kcal H-OOBu-f, 91 kcal, HO-OBu-f, 47 kcal),l which allow low-energy rearrangements to give (HO ) and O 

ni-ClPhC(O)OOH in acetonitrile will epoxidize olefins without a catalyst, but the presence of an iron complex accelerates the process by several orders of magnitude.3 

In water the Bronsted acidity of HOOH and HO- are essentially the same (pKg = 11.8 and 11.9, respectively). Electrochemical reduction of HOOH in acetonitrile yields molecular hydrogen (rather than cleavage of the HO-OH bond)4 

Hydrogen peroxide is formed from (1) the dimerization of hydroxyl radicals, 

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REACTIVITY OF HYDROGEN PEROXIDE, ALKYL HYDROPEROXIDES, AND PERACIDS... 

Reactivity of Hydrogen Peroxide, Alkyl Hydroperoxides, and Peracids... 

Reactivity of Hydrogen Peroxide, Alkyl Hydroperoxides, and Peracids (PA)2FeH + HOOH + py [(PA) FeD-OOH + Hpy+]... 

Alkyl hydroperoxides and hydrogen peroxides, which are not reactive enough to promote the Baeyer-Villiger reactions, can only be used in combination with catalysts or in the presence of carboxylic acids to form the peracids in situ [304]. 

Common alcohol oxidation methods employ stoichiometric amounts of toxic and reactive oxidants like Cr03, hypervalent iodine reagents (Dess-Martin) and peracids that pose severe safety and environmental hazards in large-scale industrial reactions. Therefore, a variety of catalytic methods for the oxidation of alcohols to aldehydes, ketones or carboxylic acids have been developed employing hydrogen peroxide or alkyl hydroperoxides as stoichiometric oxygen sources in the presence of catalytic amounts of a metal catalyst. The commonly used catalysts for alcohol oxidation are different MoAV(VI), Mn(II), Cr(VI), Re(Vn), Fe(II) and Ru complexes . A selection of published known alcohol oxidations with different catalysts will be presented here. 

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