Baeyer-Villiger oxidation, of aldehydes and

Hassall, C. W., The Baeyer-Villiger oxidation of aldehydes and ketones. Organic Reactions. 9, 73-106, 1957. 

C. H. Hassall, The Baeyer-Villiger Oxidation of Aldehydes and Ketones, Organic Reactions 9, 73 (1957). 

Iodine-catalysed hydroperoxidation of cyclic and acyclic ketones with aqueous hydrogen peroxide in acetonitrile is an efficient and eco-friendly method for the synthesis of gem -dihydroperoxides and the reaction is conducted in a neutral medium with a readily available low-cost oxidant and catalyst.218 Aryl benzyl selenoxides, particularly benzyl 3,5-bis(trifluoromethyl)phenyl selenoxide, are excellent catalysts for the epoxidation of alkenes and Baeyer-Villiger oxidation of aldehydes and ketones with hydrogen peroxide.219 Efficient, eco-friendly, and selective oxidation of secondary alcohols is achieved with hydrogen peroxide using aqueous hydrogen bromide as a catalyst. Other peroxides such as i-butyl hydroperoxide (TBHP), sodium... 

Preparing Aldehydes and Ketones A Review Introduction to Nucleophilic Addition Reactions Oxygen Nucleophiles Nitrogen Nucleophiles Mechanism Strategies Sulfur Nucleophiles Hydrogen Nucleophiles Carbon Nucleophiles Baeyer-Villiger Oxidation of Aldehydes and Ketones Synthesis Strategies... 

Supercritical CO2 is a non-polar, aprotic solvent and promotes radical mechanisms in oxidation reactions, similar to liquid-phase oxidation. Thus, wall effects might occur as known, e.g. from olefin epoxidation with 02 or H202 which may decrease epoxide selectivities. The literature covers the synthesis of fine chemicals by oxidation either without catalysts (alkene epoxidation, cycloalkane oxidation, " Baeyer-Villiger oxidation of aldehydes and ketones to esters ), or with homogeneous metal complex catalysts (epoxidation with porphyrins, salenes or carbonyls ). Also, the homogeneously catalysed oxidation of typical bulk chemicals like cyclohexane (with acetaldehyde as the sacrificial agent ), toluene (with O2, Co +/NaBr ) or the Wacker oxidation of 1-octene or styrene has been demonstrated. 

Detty et al. reported the use of selenoxide 416 as catalyst in the Baeyer-Villiger oxidation of aldehydes and ketones with [295], An example and the putative two catalytic cycles proposed are shown in Scheme 7.90. 

Mechanism of Baeyer-Villiger Oxidation Both aldehydes and ketones are oxidized by peroxy acids. This reaction, called the Baeyer- Villiger oxidation, is especially useful with ketones. 

Krow GR (1993) The Baeyer-Villiger oxidation of ketones and aldehydes. Org React (New York) 43 251-798... 

The Baeyer-Villiger Oxidation of Ketones and Aldehydes Grant R. Krow... 

Baeyer-Villiger oxidation of alkyl- and aryl-substituted C -C, cycloalkanones, steroid ketones and branched chain aliphatic ketones is catalysed by arsonated polystyrene resins [53], Larger size cycloalkanones and linear ketones react much slower. Water miscible and immiscible solvents can be used. With the latter, the resin behaves as an effective catalyst and a phase-transfer agent (triphase catalysis). The same compounds are also epoxidation catalysts. More recently, a method for the preparation of phenols by the oxidation of aromatic aldehydes and ketones has been reported. The most convenient catalysts are nitro-substituted arylseleninic acids and corresponding diselenides [54]. 

Ueno et al. (448—452) examined the catalytic activity of many MgAl-LDHs incorporating partial transition metals in the Baeyer-Villiger oxidation of ketones and cychc ketones to corresponding esters and lactones in the presence of molecular oxygen and aldehydes ... 

Krow, G. R. The Baeyer-Villiger Oxidation of Ketones and Aldehydes Organic Reactions 1993, 43,251-798. Baeyer, A. Villiger, V. Ueber die Einwirkung des Caro schen Reagens auf Ketone. Chem. Ber. 1900, 33, 858-864. 

SCHEME 159. Selenium-catalyzed Baeyer-Villiger oxidation of aromatic aldehydes and phenol formation via hydrolysis of the intermediary esters... 

Although the parent formaldehyde-derived dioxirane (H2CO2) was the first of this intriguing class of cyclic peroxides to be prepared and spectrally characterized in 1976, the conversion of aldehydes into the corresponding dioxiranes by treatment with Caroate was deemed difficult because of the expectedly facile Baeyer-Villiger oxidation of the aldehydes to their carboxylic acids. Most gratifyingly, however, is that it was recently demonstrated that optically active aldehydes may also serve as promising catalysts for asymmetric epoxidations. For example, ee values up to 94% were obtained with the aldehyde 14 as dioxirane precursor. 

TABLE 33. Results of the Baeyer-Villiger oxidation of various ketones and aldehydes using different methods... 

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