Hydrogen peroxide Baeyer-Villiger reaction

Obsolete uses of urea peroxohydrate, as a convenient source of aqueous hydrogen peroxide, include the chemical deburring of metals, as a topical disinfectant and mouth wash, and as a hairdresser s bleach. In the 1990s the compound has been studied as a laboratory oxidant in organic chemistry (99,100). It effects epoxidation, the Baeyer-Villiger reaction, oxidation of aromatic amines to nitro compounds, and the conversion of sodium and nitrogen compounds to S—O and N—O compounds. 

Quantum, by contrast, converted an ethylene—carbon monoxide polymer into a polyester-containing terpolymer by treatment with acidic hydrogen peroxide, the Baeyer-Villiger reaction (eq. 11). Depending on the degree of conversion to polyester, the polymer is totally or partially degraded by a biological mechanism. 

The Dakin reaction proceeds by a mechanism analogous to that of the Baeyer-Villiger reaction. An aromatic aldehyde or ketone that is activated by a hydroxy group in the ortho or para position, e.g. salicylic aldehyde 12 (2-hydroxybenzaldehyde), reacts with hydroperoxides or alkaline hydrogen peroxide. Upon hydrolysis of the rearrangement product 13 a dihydroxybenzene, e.g. catechol 14, is obtained ... 

Cyclobutanone annulation onto a carbonyl group translates into y-butyrolactone annulation because of the facility of the Baeyer-Villiger reaction (Eq. 68 a)8). Indeed, the reaction proceeds sufficiently rapidly that even basic hydrogen peroxide effects the oxidation whereas, with less reactive carbonyl partners, peracids must be used. 

In fluorinated alcohol solvents, nonstrained ketones such as cyclohexanone (1) undergo oxidation to lactones in the presence of hydrogen peroxide and catalytic amounts of Brpnsted acids (Berkessel and An-dreae 2001 Berkessel et al. 2002). Unlike the classical Baeyer-Villiger reaction, ketone oxidation with H2O2 in e.g. HFIP proceeds via a spiro-bisperoxide 2 intermediate (Scheme 1). In contrast to other solvents, the acid-catalyzed rearrangement of the spiro-bisperoxide 2 to two equivalents of the product lactone 3 proceeds rapidly and cleanly in HFIP. Preliminary calculations indicate active participation of the fluorinated alcohol solvent in the rate-determining step also in this case. 

Murahashi S-I, Ono S, Imada Y (2002) Asymmetric Baeyer-Villiger reaction with hydrogen peroxide catalyzed by a novel planar-chiral bisflavin. Angew Chem Int Ed 41 2366-2368... 

Bis(trimethylsilyl) peroxide, (CH3)3SiOOSi(CH3)3, is prepared from trimethylsilyl chloride, l,4-diaza[2,2,2]bicyclooctane, and Dabco s complex with 2 mol of hydrogen peroxide [127]. It is used alone [228] or in the presence of catalysts such as pyridinium dichromate [236] trimethylsilyl trifluoromethanesulfonate, CF3S03Si(CH3)3 [228, 237] or tris-(triphenylphosphine)ruthenium dichloride, [(C6H5)3P]3RuCl2 [236]. This reagent oxidizes primary alcohols to aldehydes (in preference to the oxidation of secondary alcohols to ketones [236]), ketones to esters or lactones Baeyer-Villiger reaction) [238], and nucleoside phosphites to phosphates [228]. All these oxidations require anhydrous conditions. 

Peroxyphthalic add, o-C,iH4(C02H)C03H, is obtained from phthalic anhydride and hydrogen peroxide [330] or sodium hydrogen peroxide [331] and is applied usually in ethereal solutions to epoxidations [330, 332], the Baeyer-Villiger reaction [333, 334], and oxidations of sulfides to sulfoxides [163, 335] and sulfones [336, 337]. The oxidation of sulfides to sulfones takes precedence over epoxidation, as evidenced by the fact that unsaturated ketone thioacetals are oxidized to unsaturated disulfones [337]. 

The oxidation of ketones to esters is known as the Baeyer-Villiger reaction and is effected mainly by hydrogen peroxide and peroxy acids, especially the organic peroxy acids. 

The most dependable reagent for the epoxidation of unsaturated ketones is hydrogen peroxide, especially in alkaline media [142, 143, 149, 151]. Because the Baeyer-Villiger reaction is acid-catalyzed, it does not take place during epoxidations with alkaline hydrogen peroxide or its neutral derivatives, such as fe/ t-butyl hydroperoxide [220]. Most examples of epoxidation involve unsaturated ketones with conjugated double bonds. 

Sever, R. R., Root, T. W. Computational Study of Tin-Catalyzed Baeyer-Villiger Reaction Pathways Using Hydrogen Peroxide as Oxidant. 

G.-J. ten Brink, J.-M. Vis, I. W. C. E. Arends, R. A. Sheldon, Selenium-catalyzed oxidations with aqueous hydrogen peroxide. 2. Baeyer-Villiger reactions in homogeneous solution, J. Org. Chem. 66 (2001) 2429. 

Oxidation. Hexafluoroacetone (available from Aldrich) and hydrogen peroxide form a complex which functions as a peracid. Thus it can be used in the Baeyer-Villiger reaction and for oxidation of a primary aromatic amine to a nitro compound. Preliminary results, however, indicate that the adduct is less powerful than pertrifluoroacetic acid.1... 

BAEYER-VILLIGER REACTION Hexa-fluoroacetone-Hydrogen peroxide. Hydrogen peroxide. Perphthalic add. 

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