Stereochemistry & Reaction Mechanism
Special Cases of Optical Isomers
What you already know
● Prediction of optical rotation
● Optical purity
● Enantiomeric excess
● Optical Isomerism in Even -
Cumulene and Odd - Cumulene
What you already know
● Alkylation of amine
● Biphenyl systems
● Atropisomers
● Cycloalkylidenes
● Practice questions
 Biphenyl System

A biphenyl system consists

of two phenyl rings attached
by a sigma bond.

Examples
 Biphenyl System

Biphenyls containing four large

groups in the ortho-positions cannot
freely rotate about the central bond
because of steric hindrance.

In such compounds, the two rings

are in perpendicular planes.
 Biphenyl System

In this orientation (phenyl

o-o′-tetrasubstituted biphenyls
become non-planar in order to
have minimum electronic
repulsion among the substituents.
planes
perpendicular to each other),
the free rotation of C–C single
bond is restricted, and
molecule shows optical
activity.
Enantiomers
 Biphenyl System

There is no plane of symmetry and

hence, the molecule is chiral.
 Biphenyl System

If either ring is symmetrically

substituted, the molecule has a plane
of symmetry. Hence, optically inactive.

The plane passing through the left ring will bisect the other one in two equal halves,
hence it has plane of symmetry and is achiral.
 Note!

Generally, groups in the para

position cannot cause the lack
of symmetry.
 Atropisomers

It is not always necessary for four

large ortho groups to be present
for the rotation to be prevented.
Isomers that can
be separated only
because rotation
about single bonds
is prevented. Compounds with three and even two
groups, if large enough and suitably
substituted, can have hindered rotation.
 Example

Biphenyl-2,2′-bis-sulphonic acid

Optically active.
 Is the following compound optically active?

Solution

The given compound is biphenyl. Attached groups on each phenyl (Methyl

and ethyl) are different. So, the given compound is optically active. Yes, the
given compound is optically active.
 Is the following compound optically active?

Solution

We change the attached group of fluorine to Iodine because fluorine atoms are
small and can create confusion. Now we have attached groups of NO2 and
Iodine on each phenyl. Iodine’s van der waal’s radius is similar to methyl group
and hence it will collide with NO2 group. It will also be chiral. Hence it is an
optically active compound. Yes, the given compound is optically active.
Is the following compound optically active?

Solution

Yes, the given compound is optically active.

Which of the following compounds is optically active?

B
Which of the following compounds is optically active?

D All are correct

Solution

Hence, the compound B is optically active.

Which of the following compounds is optically active?

B
 Which of the following compounds is optically active?

Solution

Hence, the compound C is optically active.

 Note!

Terphenyl

Me Et

Shows geometrical isomerism

 Does this compound shows geometrical isomerism ?

Solution

In the first phenyl ring, methyl and ethyl are different substituted groups but
in third phenyl ring, both the group attached are ethyl. Hence it will not
show geometrical isomerism.
Hence, the given compound does not shows geometrical isomerism.
 Does this compound shows geometrical isomerism ?

Solution

Although Me groups on left ring are same at both ortho positions but
presence of Br makes possible for it to show. Hence, the given compound
shows geometrical isomerism.
Does this compound shows geometrical isomerism ?

Solution

Hence, the given compound shows geometrical isomerism.

Does this compound shows geometrical isomerism ?

Solution

Hence, the given compound shows geometrical isomerism.

 Special Cases

Cumulenes Biphenyls Cycloalkylidenes

 Cycloalkylidenes

One of the double bonds in allenes is

replaced by one cycloalkane ring.

Example
Cycloalkylidenes

POS x COS x
Optically active.
Cycloalkylidenes

Enantiomeric pairs
 Does this compound shows geometrical isomerism ?

Solution

Given compound will show geometrical isomerism because when you cut the
compound from the middle it will be identical on both sides. So it can show cis-
trans conformers. But it will not show optical isomerism. Hence, the given
compound shows geometrical isomerism.
Does this compound shows geometrical isomerism ?

Solution

Hence, the given compound shows geometrical isomerism.

Does this compound shows geometrical isomerism ?

Solution

Hence, the given compound shows geometrical isomerism.

Does this compound shows geometrical isomerism ?

Solution

Hence, the given compound does not shows geometrical isomerism.

Does this compound shows geometrical isomerism ?

Solution

Hence, the given compound shows geometrical isomerism.

Does this compound shows geometrical isomerism ?

Solution

Hence, the given compound shows geometrical isomerism.

Does this compound shows geometrical isomerism ?

Solution

Hence, the given compound does not shows geometrical isomerism.

Does this compound shows geometrical isomerism ?

Solution

Hence, the given compound shows geometrical isomerism.

Find:
(i) The number of optically active compounds.
(ii) The relation between I and II.
(iii) The relation between I and III.

(I) (II) (III)

 Solution

(i) I, II and III all are optically active

(ii) I and II are pair of enantiomers
(iii) I and III are diastereomers.
 Note!

Presence of a chiral carbon is

neither a necessary nor a sufficient
condition for optical activity.

Optical activity may be present in

molecules with no chiral atom.