Stereochemistry & Reaction

Mechanism
Introducing Stereoisomerism

What you will learn

• Isomerism
• Stereoisomers
• Conformational Isomers
• Configurational Isomers
• Geometrical Isomers
• Restricted Rotation
• Conditions to Show Geometrical Isomers
• Cis-trans Configuration
• Cis-trans Configuration in Double Bond System
• Cis-trans Configuration in Cycloalkanes
 Isomerism

The phenomenon of existence

of two or more compounds
possessing the same molecular
formula but different properties
is known as isomerism.
For example : C2H6O : CH3−O−CH3
(Dimethyl ether) and CH3−CH2−OH
(Ethanol).

Such compounds are

known as isomers.
 Isomerism

Isomers

Structural Stereoisomers
(Constitutional) (Space/3D)

Chain Position

Functional Ring chain

Metamers Tautomers
 Stereoisomers

Stereoisomers have remarkably different

Isomers that are different physical, chemical, and biological properties.
from each other only in
the way the atoms are
oriented in space.

These isomers have

same connectivity of
atoms and groups.
Fumaric acid Maleic acid
M.P.: 287 oC M.P.: 138 oC
Essential metabolite Toxic, irritant
 Stereoisomers

Isomers

Structural Stereoisomers
(Constitutional) (Space/3D)

Conformational Configurational
 Conformational Isomers

There are infinite arrangements

(conformations) which arise due
to the free rotation around the
C–C 𝛔 bond, out of which different
conformations corresponding to
energy minima are called conformers.
Configurational Isomers

Isomers which differ in the

configuration i.e. the spatial
arrangement of atoms that
characterises a particular
stereoisomer.

Arises due to
non-interconvertibility
at room temperature
 Configurational Isomers

Configurational
Isomers

Geometrical Optical
Isomers Isomers
 Geometrical Isomers

Isomers which possess the same

molecular and structural formula
but differ in the arrangement of
atoms, or groups in space due to
restricted rotation. Cis Trans
 Restricted Rotation

Restricted rotation by double bond.

x- axis
>

𝛑 bond prevents rotation

because the orbitals overlap both
above and below the plane of
atoms.
Restricted Rotation

Rotation along 𝛔
𝛔 bond is
possible.

Rotation along 𝛑
𝛑 bond is not
possible.
 Restricted Rotation

Restricted rotation along 𝝈 bond of cycloalkane.

Conditions to Show Geometrical Isomers

Restricted Rotation

(ring structure)
 Conditions to Show Geometrical Isomers

Different groups should be attached

to each atom of a restricted bond.

Lone pair is also considered

1
as a distinct group.

Isotopes are considered

2
as different groups.
Conditions to Show Geometrical Isomers

Distance between two particular

group at different terminal of restricted
rotation should be different in G.I.

a≠b
 Which of the following can show geometrical isomerism?

A B

Solution

The molecule given in A will not show geometrical isomerism as both the carbons
are having the same groups. The molecule given in B is trans in nature as the groups
are different and the same groups which are attached to different carbon are on the
opposite side.
 Which of the following can show geometrical isomerism?

A B
Solution

In first molecule which is ethyne, it is linear in nature so will it will not show
geometrical isomerism. In the case of a second molecule one carbon is attached to
two hydrogen so the same groups are attached to the vinylic carbon so it will also
not show geometrical isomerism .
So, both molecule A and B will not show geometrical isomerism.
 Which of the following can show geometrical isomerism?

A B
Solution

The first molecule is but-2-ene-1,4-dioic acid. This molecule will show geometrical
isomerism as the double bonded carbons are attached to two different groups.
The second molecule is but-2-yne which is linear in structure so it will not show
geometrical isomerism.
So, only molecule A will show geometrical isomerism.
 Which of the following can show geometrical isomerism?

A B

Solution

Both molecules will show geometrical isomerism as in both the molecule

double bonded carbons are attached to different groups. So, both molecule A
and B will show geometrical isomerism.
 Which of the following can show geometrical isomerism?

A B
Solution

Molecule A is but-2-ene, in this molecule both the double bonded carbons are
attached to different groups. Molecule B is 1-phenylprop-1-ene, this molecule will
also show geometrical isomerism as double bonded carbon is attached to different
groups.
So, both molecule A and B will show geometrical isomerism.
 Will this compound show geometrical isomerism?

Solution

Since, all the atoms or groups of atoms attached on each

double bonded carbon atom are different, so it will show
geometrical isomerism.
 Will the given compounds show geometrical isomerism?

Solution

As we know, lone pair is also considered as a distinct group. So, in both molecule
doubly bonded atoms attached to two different groups so both of them will show
geometrical isomerism.
So, both molecules will show geometrical isomerism.
 Will this compound show geometrical isomerism?

Solution

Since two Cl-atoms and two Br-atoms are attached to same carbon atom it can
not show geometrical isomerism.
 Will this compound show geometrical isomerism?

Solution

Since methyl group at one carbon atom is

different from H atom present on same
carbon atom and this is found at two
different carbon atom of the ring so it can
show geometrical isomerism.
 Will this compound show geometrical isomerism?

Solution

Since methyl group at one carbon atom is

different from H atom present on same
carbon atom and this is found at four
different carbon atom of the ring so it can
show geometrical isomerism.
 Will this compound show geometrical isomerism?

Solution

Since methyl group at one carbon atom is

different from H atom present on same
carbon atom and this is found at three
different carbon atom of the ring so it can
show geometrical isomerism.
 Will the given compounds show geometrical isomerism?

Solution

As we know, lone pair is also considered as a distinct group. So, in first molecule
doubly bonded atoms attached to two different groups so both of them will show
geometrical isomerism.
Both the given compounds will show geometrical isomerism.
Will the given compounds show geometrical isomerism?

14

12
 Solution

14

12

Both the given compounds will show geometrical isomerism.

Will the given compounds show geometrical isomerism?
 Solution

Both the given compounds will show geometrical isomerism.

Will this compound show geometrical isomerism?

Solution

Yes this compound show

geometrical isomerism.
Which of the following compounds show geometrical isomerism?

A B

C D
Solution
A B

C D

Structure given in option D can not show geometrical

isomerism because the two part of the ring are same.
 Configurational
Nomenclature in G.I.
 Configurational
Nomenclature in G.I.

cis-trans Syn-Anti
 cis-trans Configuration

Configurations in
Geometrical Isomerism

1 It is used for C=C and ring.

cis trans

It is based on Same groups lie on

2 Same groups lie on the opposite sides
similarity of the group.
the same side of the of the double
double bond/ring. bond/ring
 cis-trans
Configuration in
Double bonded
Systems!
 cis-trans Configuration in Double Bond System

Examples

Same group- Same group-

same side different side

cis form trans form

 cis-trans Configuration in Double Bond System

Dichloroethene

Same group- Same group-

Same side different side

cis form trans form

 cis-trans Configuration in Double Bond System

But-2-ene

Cis-But-2-ene trans-But-2-ene

cis form trans form

cis-trans Configuration in Double Bond System
 cis-trans
Configuration in
Cycloalkanes!
 cis-trans Configuration in Cycloalkanes

Examples

trans form cis form

 cis-trans Configuration in Cycloalkanes

Examples

cis form trans form

 Predict whether the compound is cis or trans:

Solution
Predict whether the compound is cis or trans:

Solution
Predict whether the compound is cis or trans:

Solution
 Configurational
Nomenclature in G.I.

cis-trans Syn-Anti
 Syn-Anti Configuration

1 It is used for C = N, N = N Syn Anti

Same side Opposite side

It is based on similarity
2
of the group.
Syn-Anti Configuration

Anti form Syn form

 Syn-Anti Configuration

Anti

In case oximes,

If -H and -OH are

Syn
on same side

If -H and -OH are Syn

Anti
on opposite side
 Syn-Anti Configuration

How to decide the

configuration of
these oximes?
 Syn-Anti Configuration

Same side of -OH Syn-Methyl ethyl ketoxime

Opposite to -OH Anti-Ethyl methyl ketoxime

 Syn-Anti Configuration

Same side of -OH Syn-Ethyl methyl ketoxime

Opposite to -OH Anti-Methyl ethyl ketoxime

But-2-ene exhibits cis-trans isomerism due to:

Solution

A Rotation around the C2–C3 double bond

B Rotation around the C3–C4 sigma bond

C Rotation around the C1–C2 bond

D Restricted rotation around C=C bond

 Which one of the following exhibits cis-trans isomerism?

Solution
A

Hence, option C is the correct answer.

Which one of the following exhibits cis-trans isomerism?

A B

C D
 Solution

A B

C D

Hence, option A is the correct answer.