Cycloalkanones peroxidation

A large number of catalysts have been shown to be active in the oxidation of cycloalkanones to lactones using only hydrogen peroxide as the oxidant. Methyl-trioxorhenium (MTO) is moderately active in the oxidation of linear ketones [242] or higher cycloalkanones [243] but it is particularly active in the oxidation of cyclobutanone derivatives (Fig. 4.82), which are oxidized faster with MTO than with other existing methods [244]. 

Peroxysulfuric acid, PBA and MPPA, common reagents of the past, appear less frequently in the current literature. Basic 30% hydrogen peroxide or r-butylhydroperoxide have special utility for oxidation of cyclobutanones and strained, bridged cycloalkanones to lactones. Basic 3- % hydrogen peroxide is used in the Dakin oxidation of aryl aldehydes to phenols, while peroxymonophosphoric acid oxidizes aryl ketones to phenolic acetates. ... 

The system Ru(III)-EDTA catalyzes the oxidation of cyclohexane by molecular oxygen [26]. In the presence of manganese(II) acetate and molecular oxygen, alkenes and active methylene compounds react to yield cyclic peroxides [27]. a-Substituted cycloalkanones are oxidized to oxo acids by the copper(II) nitrate-dioxygen-acetic acid-water system [28a] ... 

A variation of the above reaction involves the boron trifluoride etherate-catalyzed condensation of gi OT-dihydroper-oxides 240 with dimethyl and diethyl acetals 243 (method C, Scheme 45) <2004S2356>. The gi OT-dihydroperoxides 240 were prepared from cycloalkanone dimethyl or diethyl acetals 242 by treatment with hydrogen peroxide catalyzed by boron trifluoride complexes <2003TL7359> or similarly from appropriate enol ethers <2004RCB681>. 

Ishihara developed the lipophilic Li[B(C6F5)4]-catalysed Baeyer-Villiger oxidations of various cycloalkanones with 30 wt% aqueous hydrogen peroxide (Scheme 2.3). The reaction rate was significantly accelerated with the use of oxalic acid as a cocatalyst, and the catalyst loading of the lithium salt... 

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