4.

5 Oxidative Cleavage

 KMnO4 (cold basic) and OsO4, and break only the p bond of the alkene
 Ozone and acidic KMnO4 break both the p bond and the s bond
4.5.1 Potassium permanganate (KMnO4)
1. KMnO4 in basic solution
o it is a mild oxidizing agent
o Alkene undergo a Rxn with KMnO4 in basic solution to give vicinal
diol (hydroxylated alkene)

2. KMnO4 in acidic solution

o It is a powerful oxidizing agent
o Oxidative cleavage
o Alkene undergo a Rxn with KMnO4 in acidic solution to give
carboxylic acids or ketone.
Hydroxylation of Alkenes
 Hydroxylation of Alkenes
 It is obtained by treating alkene with KMnO4 in basic solution
 Under alkaline conditions, the manganate(VII) ions are reduced to green
manganate(VI) ions . . .
o Oxidation no. Of Mn changes from +7 to +4 (from MnO4(-) ===> MnO2 in
basic medium .. change is +3)

Higher yields of the diol are obtained with osmium tetroxide (OsO4)
 Mechanism for cis-Glycol Formation

 Under the mild conditions, potassium permanganate can lead a conversion of alkenes
to glycol
 A cyclic manganese diester is an intermediate in these oxidations, which results in
glycols formed by syn addition.
Rxn Mechanism for alkene with KMnO4 in acidic or basic solution
Step 1: I is a nucleophilic addition Rxn….

Step 2: Depending on what you use for hydrolysis you can get different products:
Later for the final product formation reactions you can choose between an acid or a
base depending on your desired product! Base: Cis-Diole-product. Acid: In this
mentioned case a Dicarbonyle-compund.
Oxidative Cleavage of Alkene by KMnO4
 Under acidic conditions, the manganate(VII) ions are reduced to
manganese(II) ions.
o Oxidation no. Of Mn changes from +7 to +2 (from MnO4(-)===> Mn
(2+) in acidic medium.. change is +5
Oxidative Cleavage (KMnO4 in acid )
 With the addition of heat and/or more concentrated KMnO4, the
glycol can be further oxidized, cleaving the carbon-carbon bond.
o This leads to the formation of the mixture of ketones and
carboxylic acids.

• Sodium periodate (NaIO4) can also be used for the oxidative

cleavage of the double bond of an alkene
o to get aldehydes and ketones.
 Oxidative Cleavage of 1,2-Diols
Reaction type: Oxidation Rxn
Summary

o 1,2- or vicinal diols are cleaved by periodic acid, HIO4, into two carbonyl

compounds.
o The reaction is selective for 1,2-diols.
o The reaction occurs via the formation of a cyclic periodate ester.
o This can be used as a functional group test for 1,2-diols.
o The products are determined by the substituents on the diol.
MECHANISM OF PERIODATE CLEAVAGE OF 1,2-DIOLS
 The mechanism is not trivial, so attention here is focussed on the
actual cleavage step. Prior to this, the alcohol reacts to form a cyclic
periodate ester (shown below).
 The periodate ester undergoes a rearrangement of the electrons,
cleaving the C-C bond, and forming two C=O
4.5.2 Ozonolysis
o Ozonolysis is reaction where the double bonds of alkenes are
cleaved with ozone (O3).
o It is an oxidative cleavage reaction
o Alkanes form organic compounds in which the multiple
carbon-carbon bonds have been replaced by a carbonyl group.
 Ozonolysis is the specific reaction in which cleavage occurs and
π and σ bond. In this reaction, ozone is mainly used.
Oxidative Cleavage of Alkenes by Ozonolysis
 Ozonolysis is the specific reaction in which cleavage occurs and
π and σ bond. In this reaction, ozone is mainly used.
 In order to understand how this reaction occurs, we must first
explore the structure of ozone. Ozone is a compound with the
following resonance structures
 The gas mixture is passed through a solution of the alkene in
methanol or dichloromethane.
 Step 1: Nucleophilic addition Rxn: The first isolable intermediate
is a species called an ozonide (or molozonide).
 Step 2: Rearrangement Rxn: The molozonide is unstable and
undergoes rearrangement to produce a more stable ozonide
 Step 3: Reduction Rxn: When treated with a mild reducing
agent, the ozonide is converted into products:

 Common examples of reducing agents include dimethyl sulfide

(DMS) or Zn/H2O:
Ozonides can be cleaved to carbonyl compounds
Examples of the Oxidative Cleavage of Alkenes by Ozonolysis