Unit 2B

Stereochemistry
 Enantiomers

A pair of nonsuperimposable mirror image molecules.

Derived from the Greek word enantion, which means
opposite parts.
 Enantiomers with the formula C4H9Cl are given below.

mirror

A 1:1 mixture of enantiomers is

called a racemic mixture.

Are these two structures identical or

Cl Cl different?
H H
 Using ball-and-stick model
rotate 1800
 not all substituents coincided
(yellow balls)
 Examples of Enantiomers

Enantiomers of lactic acid drawn in two different representations

O OH HO O
C C

C C
H OH HO H
CH3 CH3

O O

OH HO
OH OH
 2-Chlorobutane Cl
CH3 CHCH2 CH3

H Cl Cl H
 3-Chlorocyclohexane

Cl Cl
 Exercise 2.6

Determine if the molecules shown below exhibits

enantiomerism.

YES!
 R and S Designations

Enantiomers are two different compounds, so they need

to be distinguished by name using the prefix R or S
arrangement of substituents about the chiral center to
the IUPAC name of the enantiomer.
R - rightward or clockwise, rectus
S leftward or counterclockwise, sinister

Naming enantiomers with the prefixes R or S is called

the Cahn-Ingold-Prelog system.
 The R and S system of specifying absolute configuration
was developed by English chemists Robert Sidney Cahn
and Sir Christopher Ingold and Swedish Vladimir Prelog in
1956.
Absolute configuration is the precise arrangement of
atoms in space at the molecular level.
Procedure for Perspective Structures
1. Rank the groups of atoms bonded to the stereogenic center,
in order of decreasing atomic number and the atom of
highest atomic number gets the highest priority (1).
 If two atoms on a stereogenic center are the same,
assign priority based on the atomic number of the
atoms bonded to these atoms. One atom of higher
priority determines the higher priority.
4

3 2

higher priority group (2)

lower priority group (3) 1
 Exercise 2.7

Assigned priority numbers.

 1

4
2

We use this as example in assigning R or S

configuration!
2. Orient the molecule with the
1
lowest priority group (4) at the
back of the molecule directly 4
2
away from you and visualize
the relative positions of the 3

remaining three groups (priority

1, 2 and 3).
3. Trace a circle from priority group 1 to 2 to 3.
If tracing the circle goes in the clockwise direction to the right,
the isomer is named R.
If tracing the circle goes in the counterclockwise direction to the
left, the isomer is named S.

enantiomer A enantiomer B
clockwise
R

counter
clockwise S
 (R)-2-butanol (S)-2-butanol

Chirality is a property of a molecule that results from

its structure due to an asymmetric carbon, tetrahedral
carbon, stereocenter or stereogenic center.
R and S designation is based on a single molecule.
 Exercise 2.8

Do the following structures represent identical molecules

or a pair of enantiomers?
 Procedure of Determining Enantiomers of Fisher
Projections

In testing for superimposability, care X

must be taken in rotating bonds in
order not to change inadvertently
the meaning of the projection.
Only two kinds of motions are allowed.
1. The structure should not be taken out of the plane of the
paper when rotated. Rotation of the structure by 180 0 is
allowed, but rotation by 900 or 2700 inverts the meaning
and will not arrive to the answer.
1. The structure should not be taken out of the plane of the
paper when rotated. Rotation of the structure by 180 0 is
allowed, but rotation by 900 or 2700 inverts the meaning
and will not arrive to the answer.

= 1800 allowed

not
90 allowed
0

X
=
2. It is permissible to keep any one group fixed and to
rotate the other three clockwise or counterclockwise.

= =
 Exercise 2.9

Classify the following pairs of Fisher projections as

identical or enantiomers .

a) and
1 2

b) and
3 4
 a) and
1 2

a) Manipulate 2 by rotating 1800 on the page.

rotate 1800

2 2 1

Only the CH3 and CHO groups are superimposable, but

not the H and Cl atoms. Thus 1 and 2 are enantiomers.
 b) and
3 4

b) Manipulate 4 by fixing the position of CHO and moving

the other three groups clockwise.
4 4 3

All four groups are superimposable with 3, so 3 and 4 are

identical (same compound).
 Exercise 2.10

Do the following structures represent identical molecules

or a pair of enantiomers by applying the procedure of
Bruice and the alternate procedure.?
 Procedure in Assigning R and S for Fisher
Projections (alternate procedure)
1. Assign priorities to the four substitutents according to
the Cahn-Ingold-Prelog rules.
2. Perform the two allowed manipulations of the Fischer
projection to place the lowest priority group at the top or
bottom.
3. If the priority of the other groups 123 is clockwise
then assign the carbon as R, if priority of the other
groups 123 is counterclockwise then assign the
center as S.
 Application: glycine
1. Assign priorities to the four substitutents according to
the Cahn-Ingold-Prelog rules.
2
1
Glycine 4
3

2. Perform the two allowed manipulations of the Fischer

projection to place the lowest priority group at the top or
bottom. 2
place at the top/below
4

1 4
900/2700

3 error
 4

2
error

1 4
1800

Rule 2: It is permissible to keep any one group fixed

and to rotate the other three clockwise or
counterclockwise with the aim of placing the lowest
priority on the top or bottom.
 4
2
H
2 1
1 4 HO2C NH2
3
3
CH3 hold steady and
rotate the other 3
1-2-3 counterclockwise groups counter-
clockwise so that 4
will be on top.

3. If the priority of the other groups 123 is clockwise

then assign the carbon as R, if priority of the other
groups 123 is counterclockwise then assign the
center as S.

(S)-Glycine
 Number of Stereoisomers

The maximum number of stereoisomers possible for a

given compound is 2n where n = number of
stereocenters.
n=1
2n = 21 = 2 stereoisomers

Larger organic molecules can have two, three or even

hundreds of stereocenters.
 Exercise 2.12

Identify the stereocenters and give the maximum number

of possible stereoisomers of the following:

Androsterone
a steroid n=7 2n = 27 = 128 stereoisomers
 Cholesterol

Only one, however, is produced by nature!

 Exercise 2.11

The following compound has only one asymmetric

carbon. Why then does it have four stereoisomers?