OXIDATION AND REDUCTION REACTION

IN ORGANIC CHEMISTRY

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• 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 C—O, C—N, and C—X bonds.

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• In organic chemistry, oxidation is seen as –
addition of oxygen and/or removal of
hydrogen. Reduction is viewed as – addition
hydrogen and/or removal of oxygen
RCH2OH [O] RCHO
R2C=O [H] R2CHOH
• Oxidizing agents bring about oxidation
while reducing agents effect reduction.
However in organic chemistry, substrate is
the focus

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• Reduction at carbon increases the number of C—H bonds or
decreases the number of C—O, C—N, or C—X bonds.

• Oxidation at carbon decreases the number of C—H bonds or

increases the number of C—O, C—N, or C—X bonds.

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 REDUCTION
• Alkenes: RR'C=CR''R''' + H2 Ni, Pd, or Pt RR'CH-CHR''R'''
• Aldehydes RCHO [H] RCH2OH; Ketones: RR'C=O [H] RR'CHOH
• Acids: RCOOH [H] RCH2OH ; Esters: RCOOR' [H] RCH2OH + R'OH
• Amides: RCONHR' [H] RCH2NHR' Nitriles: R-CΞN [H] RCH2NH2
Reagents used
• H2/catalyst: catalysts include Ni, Pd, Pt
• Metal/Acid: Examples include: Zn-Hg/HCl (Clemmensen reduction);
Fe/HCl; Fe/glacial AcOH; Sn/HCl
• Na/alcohol (Hydrogenolysis): High pressure hydrogenation. Usually
an industrial process employed in reduction of esters
RCOOR' [Na/EtOH] RCH2OH + R'OH
• Metal hydrides: Most widely used are LiAlH4 & NaBH4
- LiAlH4 is powerful and unselective (reduces virtually all groups)
- NaBH4 is mild and selective (reduces only aldehydes and ketones)

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Hydrogen, sodium borohydride, and hydrazine are the
reducing agents:

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Bromine and chromic acid are the oxidizing agents:

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 H2 as a Reducing Agent

H2, Pd on charcoal Na or Li metal in liq NaBH4 or LiAlH4

NH3

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Reduction by Catalytic Hydrogenation
Addition of two hydrogen atoms:

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Only the alkene substituted to benzene is reduced:

Reduction of carbon–nitrogen double and triple bonds:

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Reduction of Ketones and Aldehydes

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Rosenmund Reduction

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 Dissolving-Metal Reduction
Addition of an electron, a proton, an electron, and a proton:

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 Reduction by Addition of
a Hydride Ion and a Proton

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Aldehydes, ketones, and acyl halides can be reduced to
alcohols by sodium borohydrides:

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LiAlH4 is a stronger reducing agent than NaBH4

LiAlH4 is used to reduce compounds that are unreactive

toward NaBH4

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DIBALH allows the addition of one equivalent of hydride
to an ester:(Di-IsobutylAluminumHydride)

Replacing some of the hydrogens of LiAlH4 with –OR

groups decreases the reactivity of the metal hydride:

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Formation of Amines by Reduction

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NaBH4 can be used to selectively reduce an aldehyde or
a keto group in a compound:

Alkenes and alkynes do not possess a partial positive

charge:

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 Other Reduction Reactions
• Nitro reduction: Nitro groups are usually reduced by metal/acid
or H2/catalyst. However selective nitro reduction can be
achieved by using H2S in aqueous alcoholic ammonia

• Wolff-Kishner reduction: Used when Clemmensen reduction

fails or when strongly acidic conditions cannot be used
because acid-labile groups are present. It involves heating the
hydrazone or semicarbazone formed from a carbonyl with KOH
or NaOEt
Ph(R)C=O H2NNH2 Ph(R)C=N-NH2 KOH PhCH2R + N2
Hydrazine Hydrazone
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• Huang-Minlon modification (of Wolff-Kishner reduction): The
hydrazone is formed in situ by refluxing the carbonyl in
diethylene glycol with hydrazine and KOH. Advantages of this
method are:
- No need to isolate the hydrazine
- Reaction time is reduced
- Reaction can be carried out at atmospheric pressure, & large
scale
- Good yield obtained
• Meerwein-Ponndorff-Verley (MPV) reduction: is the reverse of
Oppenauer oxidation. The alkoxide commonly used is Al
isopropoxide. In order to favour the formation of alcohol,
acetone formed is removed by distillation (drives equilibrium
to the right). MPV reduction is also very selective for carbonyls
(i.e. groups such as conjugated double bond, nitro or halogen
are unaffected).
3 R(R')C=O + (Me2CH-O-)3Al (RR'CH-O-)3Al + Me2C=O22
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• Reductive amination: process by which aldehydes and ketones
are converted to 1ry amines thro’ catalytic or chemical reduction
in the presence of ammonia. An imine is formed as
intermediate.

• Birch Reduction: Benzene is reduced to 1,4-cyclohexadiene by

treating it with an alkali metal (Na, K or Li) in a mixture of liquid
NH3 & an alcohol

• Note that when benzene is hydrogenated under pressure using

H2/ metal catalyst, cyclohexane is the final product. The
intermediates – 1,3- and 1,4-cyclohexadiene, & cyclohexene
cannot be isolated since they undergo hydrogenation faster
than benzene
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Sodium borohydride can be used as a chemoselective
reducing agent:

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 +
oC
- 78
H
I B AL
D
H 2O

LiAlH4 +
Na
BH
4

H2

Raney Ni No reaction
No reaction
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 Rosenmud reduction

Na/liq.NH3

Birth rduction

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Oxidation of Alcohols

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Oxidation of a Primary Alcohol

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Mechanism of Alcohol Oxidation
by the Swern Oxidation

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Oppenauer oxidation: process by which 2ry alcohols
are oxidized to ketones using Al alkoxide (usually t-
butoxide) in the presence of a large excess of acetone
(to drive the equilibrium in the forward direction). The
process involves an initial alkoxy exchange followed
by hydride ion transfer. The reverse reaction (i.e.
reduction of ketone to 2 ry alcohol) is known as
Meerwein-Ponndorf-Verley (MPV) reduction.
3R2CHOH + (Me3C-O-)3Al (R2CH-O-)3Al + Me3C-OH

(R2CH-O-)3Al + Me2C=O 3R2C=O + (Me2CH-O-)

3Al

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Oxidation of Aldehydes and Ketones

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The Tollens reagent oxidizes only aldehydes:

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Both aldehydes and ketones can be oxidized by
peroxyacid: the Baeyer–Villiger oxidation

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 Mechanism of the
Baeyer–Villiger Oxidation

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Predicting Baeyer–Villiger reaction products:

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 Controlling Stereochemistry
in Synthesis
An enantioselective reaction forms more of one
enantiomer than of another:

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Hydroxylation of Alkenes

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Mechanism for cis-Glycol Formation

Higher yields of the diol are obtained with osmium

tetroxide than with permaganate
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Oxidative Cleavage of 1,2-Diols

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Summary of Alkene Hydroxylation Reactions

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Permaganate Cleavage of Alkenes

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Examples of permaganate-mediated alkene cleavage
reactions:

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 Oxidative Cleavage of Alkenes by
Ozonolysis

Examples:

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Structure of Ozone

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The alkene and ozone undergo a concerted six-electron
cycloaddition

Mechanism of ozonide formation:

The molozonide is unstable because it has two O—O

bonds, but the ozonide is stable

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Ozonides can be cleaved to carbonyl compounds:

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Ozonolysis Mechanism

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Examples of the Oxidative Cleavage of
Alkenes by Ozonolysis

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The benzene ring is not oxidized under mild ozonolysis
conditions:

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 Oxidative Cleavage of Alkynes
The same reagents that oxidize alkenes also oxidize
alkynes:

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 Designing a Synthesis by Functional
Group Interconversion
Conversion of an aldehyde to other functional groups:

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Conversion of a Ketone into
an Ester or an Alcohol

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