Baeyer-Villiger Oxidation Reaction is incuded in the syllabus of Advance Organic Chemistry of first semester of the M Pharm (Pharmaceutical chemistry).

1. CHHATRAPATI SHAHU JI MAHARAJ UNIVERSITY
KANPUR
TOPIC- STUDY OF BAEYER-VILLIGER OXIDATION REACTION
DIWAKAR KUMAR MISHRA
M PHARM 1ST YEAR
PHARMACEUTICAL CHEMISTRY
SCHOOL OF PHARMACEUTICAL SCIENCES
PRESENTED BY-

2. CONTENTS
• BAEYER-VILLIGER OXIDATION REACTION
• REAGENTS
• MECHANISM OF THE REACTION
• APPLICATIONS
• LIMITATIONS

3. Baeyer-Villiger Oxidation Reaction
The Baeyer–Villiger oxidation is an oxy-insertion 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.
Ketones Esters
Per acids (or)
Per acids oxo
(Involves rearrangement)
Example:

4. Reagents:
• Per acids/ peroxy acids (99% used)
• Hydrogen peroxide
• Bis- trimethyl silyl peroxide
Peroxy acid Peracetic acid

5. Examples of peracids:
R=H PFA (Peroxyformic acid)
R=CH3 PAA (Peroxyacetic acid)
R=CF3 TFPA (Trifloro peracetic acid)
R= MCPBA (Metachloro perbenzoic acid) most common

6. Mechanism:
Criegee intermediate

7. • In the first step of the reaction mechanism, the peroxyacid protonates the
oxygen of the carbonyl group.
• This makes the carbonyl group more susceptible to be attacked by the
peroxyacid.
• Next, the peroxyacid attacks the carbon of the carbonyl group forming what
is known as the Criegee intermediate.
• Through a concerted mechanism, one of the substituents on the ketone
migrates to the oxygen of the peroxide group while an carboxylic acid
leaves.
• This migration step is thought to be the rate determining step.
• Finally, deprotonation of the oxocarbenium ion produces the ester.

9. Applications:
Formation of aliphatic and aromatic esters:
3-Aminobenzophenone 3-Aminophenyl benzoate

10. • 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.
• Baeyer-Villiger oxidation is used in the synthesis of lactones, which contribute
significantly to the flavor of fruits, and unfermented and fermented dairy products.
Hence, they are used for flavor and fragrance.
• Synthesis of medicinal Compounds: Baeyer-Villiger oxidation induced by fungus
that produses Baeyer-Villiger monooxygenases, is used to transform the
dehydroepiandrosterone (androstenolone) to an anticancer agent. This reaction
was discovered in 2013 by Alina Swizdor.

11. LIMITATIONS:
• The use of peroxyacids and peroxides when performing the Baeyer–
Villiger oxidation can cause the undesirable oxidation of other
functional groups. Alkenes and amines are a few of the groups that
can be oxidized.

12. THANK YOU