4.

6 Peroxy acids based Reactions

 4.6.1 Epoxidation Rxn

 4.6.2 Baeyer-Villiger Reaction

4.6.1 Epoxidation Rxn
Epoxide formation from alkene
 Epoxides or oxacyclopropanes can be obtained by
reaction so-called epoxidation from alkenes with peroxy
acids.
 The most commonly used peroxy acids are
 meta-chloroperoxybenzoic acid (MCPBA) and
 peroxyacetic acid.
Epoxidation from alkenes with Peroxy acids
 This reaction is stereospecific.
 If we start with cis-alkene we will obtain cis-epoxide. The same
applies to trans-isomers.
Mechanism of Epoxidation of an Alkene
The addition of oxygen to an alkene is a stereospecific reaction
Oxidation of Alkenes with Peroxyacids
 When alkenes treated with a halogen in the presence of
water they will be converted into halohydrins which can be
converted further into epoxides.
 Epoxides formation from halohydrins:
o Halohydrins treated with strong base (such as
hydroxide anion) can form epoxides through with
intramolecular SN2 reaction.

 Halohydrins treated with strong base (such as hydroxide

anion) can form epoxides through with intramolecular SN2
reaction.
Mechanism of epoxide formation

 Step 1: This process achieved via an Williamson ether

synthesis. Hydroxide deprotonates the halohydrin and an
alkoxide ion is formed.
 Step 2: Then this ion acts as a nucleophile in an
intramolecular SN2 mechanism ejecting the bromide as a
leaving group.
4.6.2 Baeyer-Villiger Reaction
 When treated with a peroxyacid (RCO3H), ketones can be
converted into esters via the insertion of an oxygen atom. This
transformation called the Baeyer-Villiger oxidation.
Both aldehydes and ketones can be oxidized by
peroxyacid: The Baeyer–Villiger oxidation
 Mechanism of the Baeyer–Villiger Oxidation

The mechanism of Baeyer-Villiger oxidation

 Step 1: It starts by nucleophilic addition of the hydroperoxy group of the
peroxy acid to the carbonyl group.
 Step 2: Then a proton is intramolecularly transferred from one location to
another (rearrangement – H shift).
 Step 3: The intermediate which is formed is unstable and decomposes
through a cyclic transition state.
o The ester is obtained by alkyl rearrangement in which an alkyl group
shifts from the original carbonyl carbon to oxygen.
Important points about the Baeyer-Villiger reaction
 Treatment of a cyclic ketone with a peroxy acid yields a
cyclic ester or lactone.
 The Baeyer-Villiger oxidation with an unsymmetric
ketone is regioselective and is conditioned by the
migratory aptitude of substituents.
 Some substituents migrate more easily than others. So a
hydrogen atom will migrate more rapidly than a tertiary
alkyl group, which will migrate more rapidly than a
secondary alkyl group or phenyl, then primary alkyl group
will migrate more rapidly than a methyl group.
 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
Conversion of a Ketone into
an Ester or an Alcohol
Conversion of an Aldehyde into Other Functional
Groups