Baeyer-Villiger Oxidation Reaction

Reaction

The Baeyer–Villiger reaction involves the oxidation of ketones to esters by C-C bond cleavage of the carbonyl group and the introduction of an oxygen atom adjacent to it.1 This reaction can be accomplished using hydrogen peroxide, 3-chloroperbenzoic acid (m-chloroperoxybenzoic acid), peroxyacetic acid, or peroxytrifluoroacetic acid as the oxidizing agent. This reaction is also useful in the synthesis of lactones (cyclic esters) from cyclic ketones.

Stereospecificity and predictable regiochemistry are important features of the Baeyer–Villiger oxidation reaction. The reaction is regiospecific in nature and depends on the relative migration ability of the substituents attached to the carbonyl group. This reaction was described by Adolf von Baeyer and Victor Villiger in 1899.

 

 


An example for Baeyer–Villiger oxidation reaction:

 

 

 

Precautions

Please consult the Safety Data Sheet for information regarding hazards and safe handling practices.

Materials

     

Applications

The Baeyer–Villiger oxidation reaction is useful for the following studies:

  • Synthesis of lactones from mesomeric cyclohexanones.2
  • Synthesis of 3-hydroxyindole-2-carboxylates.3
  • Conversion of non-activated [18F]fluorobenzaldehydes to [18F]fluorophenols with high radiochemical yield.4
  • Synthesis of dibenzo-18-crown-6, dibenzo-21-crown-7, and dihydroxydibenzo-18-crown-6.5
  • One-pot chemoenzymatic synthesis of g-butyrolactones.6
  • Metal-free synthesis of vinyl acetates.7

 

Recent Research and Trends

  • The Baeyer–Villiger oxidation of cyclic ketones using aqueous hydrogen peroxide as an oxidant over transition metal oxides yields the corresponding lactones.8
  • Silica-supported tricobalt tetraoxide (Co3O4/SiO2) catalysts have been employed for the Baeyer–Villiger oxidation of cyclohexanone under Mukaiyama conditions.9
  • Submicrometer-sized tin-containing MCM-41 particles with a size of several hundred nanometers were reported as selective catalysts for the Baeyer–Villiger oxidation of adamantanone with aqueous H2O2.10
  • Chemoenzymatic Baeyer–Villiger oxidation of cyclic ketones catalyzed by Candida antarctica lipase B or Novozyme-435 suspended in an ionic liquid has been studied.11
  • Kinetic resolution of racemic 2-substituted cyclopentanones has been achieved via highly regio- and enantioselective Baeyer–Villiger oxidation.12

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