CHAPTER FIVE

STEREOCHEMISTRY: CHIRAL
MOLECULES
Number of Stereoisomers ≤ 2n
n = # of Stereogenic (chiral) centers
Chiral means four different groups around carbon atom
 away-from-you
Sawhorse projection
coming-toward-you

CH3

(Vertical / H Cl Newman projection

away-from-you coming-toward-you
( horizontal)
There is OH
a chiral C
here
 Enantiomers
have at least one chiral center
are mirror images (configuration R  S & S  R)
have no symmetry within the compound
are not superimposable (the ability for an object to be
placed over another object)

are optically active compounds

 have identical physical properties except toward the
direction of rotation of plane-polarized light

have identical chemical properties except toward chiral

reagents
 Enantiomers
mirror
OH OH
H * Cl Cl * H
CH3 CH3
A B
Not chiral
✓ because 2 H
* *

mirror
CH2OH CH2OH
H * Cl Cl * H
CH3 CH3
X Y
 Diastereomers
 have at least two chiral centers except in cis-trans
-

Geometrical Isomers
with at least one chiral center

 are not mirror images of each other

have no symmetry within the compound
are not superimposable
are optically active compounds
 have different physical properties
 have similar chemical properties
 Diastereomers

* *
* *

*
=

*
 mirror

H CH3 H CH3

H CH3 H
H3C

X Y

Geometrical Isomers
 Trans
HO OH HO OH

A B

cis-1,2-Cyclobutandiol trans-1,2-Cyclobutandiol

A & B are Diastereomers

 Meso Compounds
 are a special case of stereoisomers which
occur when a molecule has a plane of
symmetry within the compound
 are achiral compounds that contain chiral
stereogenic centers
 are superimposable (the ability for an object to
be placed over another object)

 are optically inactive

 CH3
H * OH
plane of symmetry
H * OH
CH3 meso; achiral; optically inactive

CH3
H * OH
plane of symmetry
HO * H
CH3 chiral; optically active

B
For R & S configurations, the priority of
Aldehyde, Nitrile, Alkyne, t-Butyl, Vinyl, iso-Propyl,
Ethyl & Methyl groups is:

¥;•*%%
( CH has higher atomic number
a
 away-from-you
Sawhorse projection
coming-toward-you

CH3

H * Cl Newman projection
away-from-you coming-toward-you

OH
 How to Calculate R & S Configurations
for Chiral Carbon?

 Assign a number for each group from 1 (highest priority) to 4

(lowest priority).

 Assume 4 is not there.

 Make rotation starting from 1 towards 2.
 If the rotation is clockwise (to the Right)  the initial
configuration is R.
 If the rotation is anticlockwise (to the Left)  the initial
configuration is S.
 Go back to 4.
 If number 4 is away-from-you  the configuration will be as it
is (if it is R, keep it R. If it is S, keep it S).
 If number 4 is coming-toward-you  the final configuration
will be the opposite of the initial configuration (if it is R, change it
to S. If it is S, change it to R).
 Always Rotate
S
4
1-52 & Ignore 4
4

2
H 1 H
(H3C)3C OH 3 (H C) CH
3 2 CN
2

C* C*
CH C S
CH2 O H
1
3

I S II S

3
S 1

CH3 Br
4 H * Cl 1 4 H * D 3

OH R OCH3
2 2

III S IV R
 mirror

S R

mirror R S mirror

S S S R
Enantiomers
R R R R

Same Diastereomers
Question: Assign (R) or (S) designation for the following compounds.

CH3
3
* OH 1
S
2

Br

CH3
OH
2
*
Br 1
3
S
This alone is Miso
mirror

CH3 CH3 mirror

H OH HO H plane of symmetry
H OH HO H
S R
CH3 CH3 Same Compounds
R S
A B
mirror

CH3 CH3
H OH HO H S R
HO H HO H Diastereomers
S S
CH3 CH3

X B
mirror

CH3 CH3
S R
H OH HO H Enantiomers
H OH S R
HO H
CH3 CH3

X Y
 enantiomeric excess (ee)

Racemic Mixture (50% R & 50% S):

are optically inactive compound.
4. What is the percent composition of a mixture of (S)-(+)-2-Butanol, [] = + 13.52o and of
(R)-(-)-2-Butanol, [] = - 13.52o, with a specific rotation, [] = + 5.41o?
OH
*
 Good Luck
Dr. Imad A. Abu-Yousef