Wednesday, April 22, 2020

BAEYER-VILLIGER OXIDATION

Baeyer-Villiger Oxidation





The Baeyer-Villiger Oxidation is the oxidative cleavage of a carbon-carbon bond adjacent to a carbonyl, which converts ketones to esters and cyclic ketones to lactones. The Baeyer-Villiger can be carried out with peracids, such as MCBPA, or with hydrogen peroxide and a Lewis acid.

The regiospecificity of the reaction depends on the relative migratory ability of the substituents attached to the carbonyl. Substituents which are able to stabilize a positive charge migrate more readily, so that the order of preference is: tert. alkyl > cyclohexyl > sec. alkyl > phenyl > prim. alkyl > CH3. In some cases, stereoelectronic or ring strain factors also affect the regiochemical outcome.



Mechanism of the Baeyer-Villiger Oxidation







Recent Literature


Baeyer-Villiger Oxidation of Ketones to Esters with Sodium Percarbonate/Trifluoroacetic Acid


Selenoxides as Catalysts for Epoxidation and Baeyer-Villiger Oxidation with Hydrogen Peroxide


Hypervalent λ3-Bromane Strategy for Baeyer-Villiger Oxidation: Selective Transformation of Primary Aliphatic and Aromatic Aldehydes to Formates, Which is Missing in the Classical Baeyer-Villiger Oxidation


General Metal-Free Baeyer-Villiger-Type Synthesis of Vinyl Acetates


Enantioselective Baeyer-Villiger Oxidation: Desymmetrization of Meso Cyclic Ketones and Kinetic Resolution of Racemic 2-Arylcyclohexanones


Asymmetric Baeyer-Villiger Reaction with Hydrogen Peroxide Catalyzed by a Novel Planar-Chiral Bisflavin


Conversion of Cyclic Acetals to Hydroxy Esters by MCPBA Oxidation

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