Organic Chemistry

Chapter 9
OxidationReduction
Reactions

 Oxidation is always coupled with reduction

Loss of electrons is oxidation

Gain of electrons is reduction
The oxidation state of a carbon atom equals the
total number of its CO, CN, and CX bonds

Hydrogen, sodium borohydride, and hydrazine

are the reducing agents

Bromine and chromic acid are the oxidizing agents

H2 as a Reducing Agent

Reduction by Catalytic Hydrogenation

Dissolving-Metal Reduction

Reduction by Addition of
a Hydride Ion and a Proton

LiAlH4 is a stronger reducing agent than NaBH4

LiAlH4 is used to reduce compounds that are
nonreactive toward NaBH4

DIBAL allows the addition of one equivalent of hydride to

an ester
Replacing some of hydrogens of LiAlH4 with OR groups
decreases the reactivity of the metal hydride

Formation of Amines by Reduction

NaBH4 can be used to selectively reduce an aldehyde or

a keto group in a compound

Oxidation of Alcohols

Oxidation of a Primary Alcohol

The oxidation of a primary alcohol can be stopped at the

aldehyde if pyridinium chlorochromate (PCC) is used
as the oxidizing agent

Oxidation of Aldehydes and Ketones

The Tollens Reagent Oxidizes Only

Aldehydes

Both aldehydes and ketones can be oxidized by

peroxyacid: The BaeyerVilliger oxidation

Therefore, the product of the BaeyerVilliger oxidation of

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

Oxidation of Alkenes with Peroxyacids

Mechanism of Epoxidation of an Alkene

The addition of oxygen to an alkene is a stereospecific

reaction

Hydroxylation of Alkenes

Mechanism for cis-Glycol Formation

Higher yields of the diol are obtained with osmium

tetroxide

Oxidative Cleavage of 1,2-Diols

Oxidative Cleavage of Alkenes by

Ozonolysis

The alkene and ozone undergo a concerted cycloaddition

Mechanism of ozonide formation

The molozonide is unstable because it has two OO

bonds
Ozonide is stable

Ozonides can be cleaved to carbonyl compounds

Examples of the Oxidative Cleavage of

Alkenes by Ozonolysis

A peroxyacid, OsO4, and (cold basic) KMnO4 break only

the p bond of the alkene
Ozone and acidic KMnO4 break both the p bond and the
s bond

Table 20.1 Summary of the Methods Used to Oxidize an Alkene

Oxidative Cleavage of Alkynes

O

KMnO4
CH3C

CCH2CH3

CH3C

CCH2CH3

HO O
CH3C

CCH2CH3

O3

CH3COH

O
+

CH3CH2COH

H2O
O
CH3CH2CH2C

CH

O3
H2O

CH3CH2CH2COH

CO2

Conversion of an Aldehyde into Other

Functional Groups

Conversion of a Ketone into

an Ester or an Alcohol