KOT 222

Organic Chemistry II

Chapter 12
Oxidation and Reduction

Introduction
Oxidation-reduction reactions = redox reactions.
Oxidation is always coupled with reduction and
vice versa.
Cu+ + Fe3+

Cu2+ + Fe2+

Cu+ Cu2+ + e-

Loss of electrons is oxidation

Fe3+ + e- Fe2+

Gain of electrons is reduction

Relative number of C-H and C-Z bonds

determine whether an organic compound is
oxidized or reduced.
(Z=element more electronegative than C: O, N and halogen)

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

Reduction Reactions
Reducing agents:
Provide the equivalent of two hydrogen atoms.
Hydrogen, sodium borohydride, and hydrazine
are the reducing agents.

Types of reductions
1. Catalytic hydrogenation
Using molecular H2 as reducing agent in the
presence of a metal catalyst.
2. Dissolving metal reduction
Addition of two protons and two electrons to the
substrate. Alkali metals as a source of electrons,
and liquid ammonia as a source of protons.
3. Hydride reducing agents: NaBH4, LiAlH4
Addition of H2 is done by adding a hydride (H)
and a proton (H+).

Reduction of Alkenes Catalytic

Hydrogenation

Occurs only in the presence of a metal catalyst.

The catalyst consists of a metalusually Pd, Pt,
or Ni, adsorbed onto a finely divided inert solid,
such as charcoal.
H2 adds in a syn fashion.

Mechanism
The surface of the catalyst binds both H2 and the alkene. H2 is
transfer to the bond in rapid stepwise process.

 The mechanism explains two facts about hydrogenation:

Hydrogenation and alkene stability

Heat of hydrogenation, Ho can be used as a measure of the
relative stability of two different alkenes that are
hydrogenated to form the same alkane.

When hydrogenation of two alkenes gives the same alkane,

the more stable alkene has the smaller heat of hydrogenation.

Hydrogenation of other double bonds

With Raney Ni, any

double bond in the
compound will be
reduced.

Hydrogenation of oils
When unsaturated vegetable oil is treated with hydrogen, some
or all of the bonds add H2. This increases the melting point of
the oil.
Margarine is prepared by partially hydrogenating vegetable oils
to give a product with a consistency that more closely resembles
butter.

Reduction of Alkynes
H2 is added to the one or both of the bonds.
Three different ways:

Reduction of an alkyne to an alkene

With H2 and a Pd catalyst.

Syn addition

Reduction of an alkyne to a cis alkene

Use less active Pd catalyst Lindlar catalyst.
Deactivated or poisoned

A stereoselective reaction, only one stereoisomer is

formed.
1 equivalent

Reduction of an alkyne to a trans alkene

In a dissolving metal reduction (such as Na in NH3), the
elements of H2 are added in an anti fashion to form a
trans alkene (stereoselective).

Involves the sequential addition of electrons and protons to

the triple bond.

Mechanism:
Step 1 & 2: Addition of one electron and one proton to form
a radical

Step 3 & 4: Addition of one electron and one proton to form

the trans alkene

Why only trans alkene is formed?

The vinyl carbanion formed is more stable when
the larger R groups are farther away from each
other to avoid steric interactions.

Summary of Alkyne Reductions

Reduction of Polar CX Bonds

Alkyl halides can be reduced to alkanes with

LiAlH4.
Epoxide rings can be opened with LiAlH4 to form
alcohols.

Mechanism
A nucleophilic substitution reaction.
H- from LiAlH4serves as a strong nucleophile.

This reaction follows an SN2 mechanism.

Unhindered CH3X and 1 alkyl halides are more easily reduced
than more substituted 2 and 3 halides.
In unsymmetrical epoxides, nucleophilic attack of H occurs at
the less substituted carbon atom.

LiAlH4 is a stronger reducing agent than NaBH4

LiAlH4 is used to reduce compounds that are
nonreactive toward NaBH4

Mechanism (not in syllabus)

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

Oxidation Reactions
Oxidizing agents
Two main categories:
1. Reagents that contain an oxygen-oxygen bond
O2, O3 (ozone), H2O2 (hydrogen peroxide),
(CH3) 3COOH (tert-butyl hydroperoxide), and
peroxyacids (RCO3H).

mCPBA and MMPP are used to convert alkene to an epoxide.

2. Reagents that contain metal-oxygen bonds

The most common oxidizing agents with metal-oxygen
bonds contain either chromium +6 (six CrO bonds) or
manganese +7 (seven MnO bonds).
Example: CrO3, Na2Cr2O7 and K2Cr2O7, and PCC.

The most common Mn7+ reagent is KMnO4 (potassium

permanganate).
Other oxidizing agents that contain metals include OsO4
(osmium tetroxide) and Ag2O [silver(I) oxide].

Oxidizing Reactions

Epoxidation
The addition of an oxygen atom to an alkene to
form an epoxide.
Usually with peroxyacid.

Mechanism
A concerted addition of
one O atom of the
peroxyacid to the
bond.

Epoxidation occurs via syn addition of an O atom to either

side of a planar double bond.

Stereochemistry of epoxidation
Epoxidation is stereospecific because cis and trans
alkenes yield different stereoisomers as products.
A cis alkene gives an epoxide with cis substituents. A
trans alkene gives an epoxide with trans substituents.

(50/50%, racemic mixture)

29

Dihydroxylation
Addition of two hydroxy groups to a double
bond, forming a 1,2-diol or glycol.
It can be an anti addition or syn addition.

Anti dihydroxylation
Achieved in two steps - epoxidation, followed by
ring opening with OH or H3O+.

Syn Dihydroxylation
Results when an alkene is treated with either
KMnO4 or OsO4.

Mechanism
1.
2.

Each reagent adds two oxygen atoms in a syn fashion.

Hydrolysis of the cyclic intermediate cleaves the metal
oxygen bonds, forming a cis-1,2-diol.

Dihydroxylation can also be carried out by using a catalytic

amount of OsO4, if the oxidant N-methylmorpholine N-oxide
(NMO) is also added.
In the catalytic process, dihydroxylation of the double bond
converts the Os8+ oxidant into an Os6+ product, which is then
re-oxidized by NMO to Os8+.

Oxidative Cleavage of Alkenes

Breaking of the double bond of an alkene to
form two carbonyl groups.
Cleavage with ozone (O3) is called ozonolysis.

Mechanism
The alkene and ozone undergo a concerted
cycloaddition.
The unstable ozonide is reduced to afford carbonyl
compounds with Zn (in H2O) or dimethylsulfide
(CH3SCH3).

(unstable)

oxidative cleavage involves a

double bond that is part of a
ring, the ring opens up affording
a single chain with two
carbonyls at the carbons where
the double bonds were originally.

Mechanism (not in syllabus)

Oxidative Cleavage of Alkynes

Alkynes undergo oxidative cleavage of the and
both bonds.
Internal alkynes are oxidized to carboxylic acids
(RCOOH).
Terminal alkynes afford a carboxylic acid and CO2
from the sp hybridized CH bond.

Oxidation of Alcohols
Alcohols are oxidized to a variety of carbonyl
compounds.

Recall that the oxidation of alcohols to carbonyl compounds

is typically carried out with Cr6+ oxidants, which are reduced
to Cr3+ products.
CrO3, Na2Cr2O7, and K2Cr2O7 are strong, nonselective
oxidants used in aqueous acid (H2SO4 + H2O).
PCC is soluble in CH2Cl2 (dichloromethane) and can be used
without strong acid present, making it a more selective,
milder oxidant.

Oxidation of 2 Alcohols
Any of the Cr6+ oxidants effectively oxidize 2 alcohols to
ketones.

Mechanism:

Oxidation of 1 Alcohols
1o alcohol oxidized to aldehydes under mild reaction
conditions using PCC in CH2Cl2.
1o alcohol oxidized to carboxylic acid under hasher
reaction conditions - CrO3, Na2Cr2O7, and K2Cr2O7 in the
presence of H2O and H2SO4.

Mechanism:

Cr6+ oxidations are characterized by a color change, as the redorange Cr6+ reagent is reduced to green Cr3+.

Green Chemistry Oxidation of Alcohols

To avoid the usage of toxic (OsO4 and O3) and
corrosive (H2SO4) reagents.
To avoid the generation of carcinogenic byproducts (Cr3+).
Use a polymer supported Cr3+ reagent
Amberlyte A-26 resin-HCrO4.

Heating the insoluble polymeric reagent with an alcohol results

in oxidation to a carbonyl compound, with formation of an
insoluble Cr3+ by-product which can be regenerated and
reused in a subsequent reaction.

Sharpless Epoxidation
an achiral starting material has reacted with an
achiral reagent to give either an achiral product,
or a racemic mixture of two enantiomers.

K.Barry Sharpless, reasoned that using chiral

reagent might make it possible to favor the
formation of one enantiomer over the other.

In the Sharpless epoxidation, the double bonds of allylic

alcohols are oxidized to epoxides.
Since the formation of only one enantiomer is favored, the
reaction is said to be enantioselective.
An enantioselective reaction affords predominantly or
exclusively one enantiomer.
A reaction that converts an achiral starting material into
predominantly one enantiomer is called an asymmetric reaction.

tert-butylhydroperoxide (CH3)3COOH; a titanium catalystusually

titanium(IV) isopropoxide, Ti[OCH(CH3)2]4; and diethyl tartrate (DET).

What determine the product in Sharpless epoxidation?

The identity of the DET isomer,
(+)-DET or (-)-DET determines
which enantiomer is the major
product
obtained
in
the
epoxidation.

 To determine which enantiomer is formed from a given

isomer of DET, draw the allylic alcohol in a plane, with C=C
horizontal and the OH group in the upper right hand corner;
then:

Exercises

H
CH2OH
C

H3C

Sharpless reagents
(+)-DET

H
H
C
H3C

C
CH2OH

Sharpless reagents
(+)-DET

CH2OH

Sharpless reagents
(-)-DET

Home Work Tutorial Questions

12.41,12.46, 12.56,12.62, 12.73