How do we “name” an enantiomer?

A problem......How can we look at two Lewis structures

and decide if they represent two identical compounds or
a pair of enantiomers? How can we name them?
C 2H 5 C 2H 5

H Cl Cl H

CH3 CH3
R.S. Cahn, C.K. Ingold and V. Prelog, The specification of asymmetric
configuration in organic chemistry, Experientia, 1956, 12, 81

Configuration means how atom or group of atoms are

arranged around a stereocenter in stereoisomers
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Cahn – Ingold - Prelog rules
Absolute Configuration
Step 1: assign a priority to the 4 atoms or groups of atoms
bonded to the tetrahedral stereogenic center:
i. If the 4 atoms are all different, priority is
determined by atomic number. The atom
of higher atomic number has the higher
priority.
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ii. If priority cannot be determined by (i), it H H H H
is determined by a similar comparison of H C C C H
atoms working out from the stereocentre. H H Cl H
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In the methyl group, the second atoms are H, H, H whereas in the
ethyl group, they are C, H, H.
The priority sequence is therefore Cl, C2H5, CH3, H.
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Cahn – Ingold - Prelog rules
iii. A double or triple bond to an atom, A, is considered
as equivalent to two or three single bonds to A:

The sequence is therefore -OH, -CHO, -CH2OH, -H.

• Other common multiple bonds are drawn below:

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Cahn - Prelog - Ingold rules
Step 2: Arrange the molecule so that the group of lowest priority
is pointing away from you and observe the arrangement of the
remaining groups:

Br Br

S R

Cl I I Cl
H H
If, on going from the group of highest priority to that of second
priority and then to the group of third priority, we go in a
clockwise direction, the enantiomer is designated as R and if
we go in a counter-clockwise direction, the enantiomer is
designated as S.
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 Stereochemistry H3C CH3 H3C CH3
4 H CH3 H3C
H
11 1
F H 4 F
3 2F H 2
CH3
H3 H3C CH3 H3C
H3C
(R)-2-Fluorobutane 3 2 (R)-2-
(R)-2-fluorobutane
(S)-3-tert-butylcyclohexene

(S)-3-tert-butylcyclohexene

O
1 4
3
Br H
H 2 CH3
H3C CH3 HO CH3 H3C
2 3 1 4
(R)-carvone
(S)-4-bromo-2-methyl-1-pentene (S)-4-bromo-
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(R)-2-hydroxy-2-methyl-butanal
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Molecular Symmetry and Chirality
1. Plane of symmetry (σ)
• A plane bisects a molecule so that one half of molecule is
the mirror image.
• All atoms in a molecule are on a plane

2. Center of symmetry (i): F Cl

If any straight line passes a atom and
molecular center, the same atom or H H
group is encountered on the site at equal H H
distance but in the opposite direction.
Cl F
Any molecule with a plane of symmetry or a
center of symmetry is achiral molecule. 6
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Multiple Stereocenters
3-Chloro-4-methylhexane There are two chiral centers

Enantiomer

What about this

relationship?
CH3

Enantiomer
Cl
(3R, 4R)
They have diastereomeric relationship. Stereoisomers that are not
enantiomers (non-superimposable mirror images) are called
diastereomers. Diastereomers have different physical properties
n chiral centers  2n maximum stereoisomers 7
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Multiple Stereocenters
How many stereoisomers for 2,3,4-trichlorohexane?
Asymmetric centers n = 3; 2n = 8
CH3 CH3 CH3 CH3
S H Cl Cl H R H Cl Cl H
S H Cl Cl H R H Cl Cl H
R H Cl Cl H S Cl H H Cl
CH2CH3 CH2CH3 CH2CH3 CH2CH3

CH3 CH3 CH3 CH3

H Cl Cl H Cl H H Cl
Cl H H Cl H Cl Cl H
H Cl Cl H H Cl Cl H
CH2CH3 CH2CH3 CH2CH3 CH2CH3
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Multiple Stereocenters
3,4-Dichlorohexane

Enantiomer Meso compound

??

A meso compound is one which is superimposable on its mirror

image even though it contains stereogenic centres. The molecule
is achiral. 9
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