Hydrogenation-Baeyer-Villiger

Tandem hydrogenation-Baeyer-Villiger oxidation reaction catalysed by rhodium catalysis and biocatalysis. 

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. 

When a ketone 1 is treated with hydrogen peroxyde or a peracid, a formal insertion of oxygen can take place to yield a carboxylic ester 2. This process is called the Baeyer-Villiger oxidation ... 

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 ... 

Urea hydrogen peroxide adduct (UHP) was employed in metal-catalysed asymmetric epoxidation [98] and Baeyer-Villiger oxidation [99,100]. Since the presence of urea does not change the course of the reaction, this will not be described here. Conversion of epoxides to halohydrins with elemental... 

For the oxidation of ketones, Baeyer-Villiger oxidation of cyclic ketones with monopersuccinic acid in water gives lactones in good results (Eq. 8.22).47 Peroxy species generated from borax in 30% hydrogen peroxide is effective for the Baeyer-Villiger oxidation of... 

The carbon templated tin incorporated mesoporous silicalite catalysts with MFI structure were successfully synthesized using microwave and well characterized using all the physico-chemical techniques. The catalytic activity of these catalysts was studied for liquid phase Baeyer-Villiger oxidation of various cyclic ketones using hydrogen peroxide. All the catalyst showed high conversion ( 100%) for bicyclic ketones with 100% selectivity to the corresponding lactone. 

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. 

To date, reports have involved palladium catalysts for Suzuki and Sono-gashira coupling reactions [63-66], rhodium catalysts for silylations of alcohols by trialkylsilanes [67,68], and tin-, hafnium-, and scandium-based Lewis acid catalysts for Baeyer-Villiger and Diels-Alder reactions [69]. Regardless of exact mechanism, this recovery strategy represents an important direction for future research and applications development. Finally, a particularly elegant protocol where CO2 pressure is used instead of temperature to desorb a fluorous rhodium hydrogenation catalyst from fluorous silica gel deserves emphasis [28]. 

Oxidation of aryl aldehydes or aryl ketones to phenols using basic hydrogen peroxide conditions. Cf. Baeyer-Villiger oxidation. 

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