Cycloalkanones Baeyer-Villiger oxidations

One of the first examples of Baeyer-Villiger reactions to be reported involved the oxidation of menthone using Caro s acid. The Baeyer-Villiger oxidation of cycloalkanones (Eq. 26) using trifluoroperoxyacetic acid generated by the inter-... 

All these degradation pathways were shown to involve a Baeyer-Villiger oxidation of a cycloalkanone that led to formation of the corresponding lactone. Further degradation then occured via hydrolysis of this lactone by a lactone hydrolase which has, in some cases, been isolated. As an example, the reaction sequence for the degradation of cyclopentanol by Pseudomonas sp. NCIMB 98721351 is shown in Fig. 16.5-7. 

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]. 

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... 

Scheme 2.3 Baeyer-Villiger oxidation of cycloalkanones with the use of Li[B(C6Fs)4].

Adger B, Bes MT, Grogan G, McCague R, Pedragosa-Moreau S, Roberts SM, Villa R, Wan PWH, Willetts AJ. Application of enzymic Baeyer-Villiger oxidations of 2-substituted cycloalkanones to the total s3mthesis of (R)-(+)-lipoic acid. J. Chem. Soc., Chem. Commun. 1995 1563-1564. 

Use of the Baeyer Villiger reaction for the oxidation of cycloalkanones to lactones 04CRV4105. 

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