Chiral center or tetrahedral stereocenter

In 2-butanol, atom C2 is attached to four different groups. C2 atom is a chiral center

or tetrahedral stereocenter. A molecule containing a chiral center or tetrahedral
stereocenter and its mirror images are nonsuperimposable. They are configurational
stereoisomers. They are called enantiomers.

 Example: 2-butanol
I and II are mirror
images of each other
(figures a and b)
I and II are not
superposable and so
are enantiomers (figure
Both molecules I and
c) II are having a chiral
centre or tetrahedral
stereocenter.
2-butanol
is a chiral
Molecule II is mirrormolecule
image of molecule I.
They are not superimposable.
They are different only in the way their atoms
are oriented in space. They are stereoisomers.
They are called enantiomers.
Non-superimposable, mirror image isomers are
called Enantiomers.

Enantiomer

Enantiomers are related to each other as a right hand is

related to a left hand and result whenever a tetrahedral
carbon is bonded to four different substituents.

Tests for chirality

A chiral molecule should have atleast a tetrahedral stereocenter.
A chiral molecule does not possess a plane of symmetry.
A chiral molecule and its mirror image are not superimposable.

Chirality
Chirality is the property of the entire molecule, whereas a
tetrahedral stereocenter (also called as chirality center or
tetrahedral stereogenic center or chiral center) is a structural
feature within the molecule that gives rise to the chirality.

Achiral molecules
A molecule is not chiral (ky-ral, from the Greek cheir,
hand) if it contains a plane of symmetry (plane that cuts
through the middle of an object or molecule in such a way
that one half of it is a mirror image of the other half)

Achiral molecules
Cl

Representation of Stereoisomers
How do we represent a three
dimensional molecule on to a two
dimensional plane?
Wedge-and-dash drawing

Cl
F
H

Br

Representation of Stereoisomers
Fischer projection formula (also called
cross formula).
Provides a rapid means of depicting
molecules with chiral carbons.

Allows for convenient comparison of

stereochemistry especially when more
than one chiral carbon exists.
9

Fischer Projection Formula

How is Fischers formula drawn?

We draw two lines [one vertical and

one/(two or more) horizontal line(s)]
depending
upon
the
number
of
stereocenter/(s) in the molecule.
The point of intersection of these lines is
considered
as
representing
the
stereocenter.

The formula can be drawn only for

molecules with stereocenter.
10

Fischer Projection Formula

In the Fischer projection, the horizontal bonds to
the chiral center are always above the plane and
the vertical bonds to the chiral center are below
the plane. (the horizontals are hugging you.)

11

ABSOLUTE CONFIGURATION
Configuration means how atom or group of
atoms are arranged around a stereocenter
in stereoisomers.
It is represented (specified) by letter R or
S.
For doing this, we assign priority numbers
to the atoms/groups attached to the
stereocenter according to Cahn-IngoldPrelog (CIP) system and see which way the
priority numbers are arranged.

SEQUENCE RULE
1. The atom of highest atomic number gets
the highest priority (1).

(1)

(6)

-H

-CH3

(7)

-N H2

(8)

(16)

- OH

- SH

(17)

(35)

(53)

- Cl

- Br

-I

Increasing priority
13

SEQUENCE RULE
2. If two atoms on a stereocenter are
the same, assign priority based on
the atomic number of the atoms
bonded to these atoms.

14

SEQUENCE RULE

(1)

- CH 2 -H

(6)

- CH 2 -CH 3

(7)

- CH 2 -N H2

(8)

- CH 2 -OH

Increasing priority
15

SEQUENCE RULE
3. If two isotopes are bonded to the
stereocenter, then the atom of highest
mass number gets the highest priority.

16

SEQUENCE RULE
4. To assign a priority to an atom that is
part of a multiple bond, treat a multiply
bonded atom as an equivalent number
of singly bonded atoms.

17

Sequence Rule 4:

(O) (C)

CH2 CH

(N) (C)

H C

(N) (C)

(C) (C)

HC C H
C
C C C
C
C
H
C C
C
C
H H

ASSIGNING CONFIGURATION
1. Locate the chiral center, identify its
four substituents, and assign priority
from 1 (highest) to 4 (lowest) to each
substituent.
2. Orient the molecule so that the group
of lowest priority (4) is directed away
from you.
3. Read the three groups projecting
toward you in order from highest (1) to
lowest priority (3).
19

ASSIGNING CONFIGURATION
If the groups are read clockwise, the
configuration is R; if they are read
counterclockwise, the configuration is S
1

4
3

(rectus)

3
S

(sinister)

ASSIGNING CONFIGURATION

21

ASSIGNING CONFIGURATION

22

ASSIGNING CONFIGURATION
CH3

CH2CH3
OH

H3C
H

CH2CH3

H
OH

23

Assigning Configuration Drawing

Fischer Projection Formula

1
OH

1
2
CH2CH3

3
H3C
A

1
3
CH3

H4

R isomer

H 4
1
OH

2
H3CH2C
B

3
4

S isomer

Assigning Configuration Drawing

Fischer Projection Formula
CH3

CH2CH3

H3C

OH

H A

2
CH2CH3
4
H

3
H3C
A

CH2CH3

OH

2
H3CH2C

H3CH2C 2

R isomer

1
OH

3 CH3

1
OH
H4

OH 1

4
H

3
H3C

1
OH

2
H3CH2C

3
CH3
H 4

S isomer

ASSIGNING CONFIGURATION
If the lowest priority number is along
vertical line (may be above or below) then
assigned specification remains same.
If the lowest priority number is along
horizontal line (on the left or right of the
stereocenter) then assigned specification
will be opposite to the specification we
get.
26

Molecules with More than One Stereogenic Center

The maximum number of stereoisomers

available will not exceed 2n, where n is equal to
the number of tetrahedral stereogenic centers

Here n = 2, so expected number of stereoisomers = 4

Stereoisomers of 2,3-dibromopentane

Structures 1 4 are all different, so there are, in total four stereoisomers of

2,3-dibromopentane.
1 and 2 are non-superimposable and mirror-images of each other Enantiomers.
Isomer 3 is obtained by changing the configuration at C2 of isomer 1.
3 and 4 are non-superimposable and mirror-images of each other Enantiomers.
1 and 3 are non-superimposable and they are not mirror-images of each other they
are diastereomers.
Similarly, 2 and 4 - diastereomers.
1 and 4 - diastereomers.
2 and 3 diastereomers.

Conventions to be followed while drawing three

dimensional formulas for molecules with
more than one stereogenic center
Convention 1: Write structures in eclipsed conformations. It is
easy to recognize planes of symmetry when they are present.
Convention 2: Write the longest carbon chain in a vertical
orientation on the page. This makes the structures directly
comparable.

Stereoisomers of 2,3-dibromobutane
Two chiral centers. Four stereoisomers expected, three
observed.

Molecules A and B are Enantiomers.

Meso Compounds
Sometimes molecules with 2 or more chiral centers will
have less than the maximum number of stereoisomers.

C and D are two molecules of same compound.

Meso Compounds
Meso compound: achiral despite the presence of
chiral centers
Not optically active
Superposable on its mirror image
Has a plane of symmetry

Tartaric acid

33

Fischer Projection Formulas for Compounds Containing

More Than One Chiral Centers

Conventions: Main carbon chain extends from top to bottom. All atoms/groups eclipsed.
Vertical lines represent bonds that project behind the plane of the screen. Horizontal
lines represent bonds that project out of the plane of the screen.

The intersection of vertical and horizontal lines represents a carbon atom, usually one
that is a chiral center.