BAEYER VILLIGER REACTION

By
Dr. Sabita Nayak
Department of Chemistry
Ravenshaw University
Cuttack
07-11-2020
 BAEYER VILLIGER OXIDATION REACTION

The Baeyer–Villiger oxidation is an organic reaction that forms

an ester from a ketone or a lactone from a cyclic ketone,
using peroxyacids or peroxides as the oxidant. 
The reaction is named after Adolf Von Baeyer and Victor Villiger who first
reported the reaction in 1899

Adolf von Baeyer Victor Villiger

 Reaction is stereospecific.
 Oxygen insertion occurs with retention of configuration.
 BAEYER VILLIGER REACTION

Solvents used: glacial acetic acid and chloroform

BAEYER VILLIGER REACTION
 Mechanism for Bayer Villiger Oxidation
Nucleophilic attack of peracid on the protronated ketone gives an
intermediate peroxide (i). The peroxide then undergoes loss of
carboxylate anion and migration of a group from carbon to electron
deficient oxygen atom to yield the protonated ester (ii). Finally loss
of proton gives ester.
O

O OH R2 C
H OH O OH
R2CO3H
R C R C R C O O C R2 O
R C O
R1 R1
R1 R1
(i)

OH OH
O
-H
R C OR 1 R C OR 1 R C OR1
 Migratory apptitude
In unsymmetrical ketone, that group migrates which is more electron
releasing.
Thus migratory aptitude of alkyl groups is in the order

Electron releasing substituents in aryl groups facilitate migration.

Hence the migratory order of aryl groups is
p-anisyl > p-tolyl > phenyl > p-chlorophenyl > p-nitrophenyl
In case of alkyl aryl ketone, aryl group migrates.

Therefore, the product of the Baeyer–Villiger oxidation of cyclohexyl methyl

ketone will be cyclohexyl acetate, because a secondary alkyl group is more
likely to migrate than a methyl group
 Bayer Villiger Oxidation

 Peroxymonosulfuric acid
APPLICATIONS
APPLICATIONS
APPLICATIONS
 Application
 Synthesis of esters
 Synthesis of anhydrides
 Synthesis of lactones
O O
CF3CO3H
CH3 C C(CH 3) 3 CH 3 C OC(CH3)3

Pinacolone t-butylacetate
O O
O RCO3H O
O

-Naphthaquinone

O O
RCO3H O

Cyclohexanone Caprolactone
Limitation of Bayervilliger Oxidation Reaction
 APPLICATION
Zoapatanol is a biologically active molecule that occurs naturally in the zeopatle plant,
which has been used in Mexico make a tea that can induce menstruation and labor.
In 1981, Vinayak Kane and Donald Doyle Reported a synthesis of zoapatanol.
They used the Baeyer–Villiger oxidation to make a lactone that served as a crucial
building block that ultimately led to the synthesis of zoapatanol
Kane and Doyle used a Baeyer-Villiger oxidation to synthesize zoapatanol
 Synthesis of steroid

In 2013, Alina Świzdor reported the transformation of the steroid dehydroepiandrosterone

 to anticancer agent testololactone by use of a Baeyer–Villiger oxidation
induced by fungus that produces Baeyer-Villiger monooxygenases.