Chapter 4

Chirality

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Section 4.1

INTRODUCTION TO CHIRALITY:
ENANTIOMERS
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Chirality
A molecule is chiral if its two
mirror image
forms are not
superimposable upon one
another.

A molecule is achiral if its

two mirror image
forms are superimposable.

Mirror Mirror: Chirality in Medicine

Sedative,
reduces
nausea

(R)-Ibuprofen

Severe
birth
defects

(S)-Ibuprofen
Active compound

Chirality
A chiral molecule is:
not identical to its mirror image
not superimposable on its mirror image in three dimensions

An achiral molecule is
superimposable on its mirror image

chiral

Bromochlorofluoromethane

A and B are
enantiomers:
mirror images that
are not identical.

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Chirality & Enantiomers

Molecules A and B are mirror images and not
superimposable on one another
To show
nonsuperimposability,
rotate this model 180
around a vertical axis.

It is impossible to align
all five atoms in A and B.
A and B are both chiral.
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Identical Mirror Images

Many molecules are identical to their mirror images
To test, reflect the molecule through a mirror and try to
superimpose the mirror image on the original
We can simply slide the mirror image on top of the
original to see that CHClF2 is achiral.

Chlorodifluoromethane

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Isomers

Cons.tu.onal Isomers:
How atoms are connected

Enan.omers
Uniden.cal mirror images

Stereoisomers:
3D posi.on of atoms

diastereomers

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Section 4.2

THE CHIRALITY CENTER

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The Chirality Center

A carbon bonded to four different groups w z is called a
chirality center, or asymmetric center, or stereocenter,
or stereogenic center

When w z are all different, Cwxyz is a chiral compound

A chirality center can be used to identify a compound as
chiral
Molecules with more than one
chirality center may be achiral!
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Chirality and Chiral Centres

CH3
CH3CH2CH2

CH2CH2CH2CH3

CH2CH3

chiral

OH

Linalool: naturally occurring alcohol

in owers & spices used in cosme>cs

chiral

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Chirality Centers in Rings

Note that any differences in ring groups make them
distinct for the purposes of identifying chirality centers

*
1,2-Epoxypropane

The starred carbon is a chirality center. It is bound

to four different groups: CH3, CH2O, H, and OCH2

Limonene

Carbon 4 is a chirality center. It is attached to:

H; CH2CH2 ; CH2CH= ; C=
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Section 4.3

SYMMETRY IN ACHIRAL
STRUCTURES
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Elements of Symmetry
Any molecule with a plane of symmetry
or a center of symmetry must be achiral.
Plane of symmetry: bisects a molecule into 2 mirror
image halves

Inversion center: a point through which all atoms are

projected

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Plane of symmetry

A plane of symmetry bisects a molecule into two

mirror image halves.
1-Bromo-1-chloro-2-fluoroethene has a plane
of symmetry.

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Center of symmetry
A point in the center of the
molecule is a center of
symmetry if a line drawn
from it to any element,
when extended an equal
distance in the opposite
direction, encounters an
identical element.

Which molecules are

chiral vs. achiral?
A)

B)

Br

C)

Br

HO

HO

achiral

Br
chiral

Br

achiral

 A substance is optically active if it rotates

the plane of polarized light.
In order for a substance to exhibit optical
activity, it must be chiral and one enantiomer
must be present in excess of the other.
Section 4.4

OPTICAL ACTIVITY

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Rotation of Plane-polarized Light

Chiral compounds containing an excess of one
enantiomer over the other rotate the plane of planepolarized light
Optical rotation can be measured using two polarizing
filters, one of which rotates

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Specific Rotation & Enantiomeric Excess

Pure (+) enantiomer rotates light in one direction; pure ()
enantiomer rotates light to the same angle in the opposite
direction
Optical rotation depends on the path length (l) and concentration
(c) of the sample; we can divide out these variables to obtain
specific rotation ([])

[] = 100
cl

concentration = g/100 mL
length in decimeters
() is observed rotation

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Specific Rotation: How Sweet it is!

hDp://www.rsc.org/Educa>on/EiC/issues/2012January/chirality-in-sugars.asp
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Racemic Mixture
A mixture containing equal quantities
of enantiomers is called a racemic mixture.
A racemic mixture is optically inactive.
( = 0)
A sample that is optically inactive can be
either an achiral substance or a racemic
mixture.

Optical Purity
An optically pure substance consists exclusively
of a single enantiomer.
Enantiomeric excess (ee) =
% one enantiomer % other enantiomer
% optical purity = enantiomeric excess
The specific rotation of a mixture of (+) and ()
enantiomers is linearly related to [] for the pure
enantiomer and the enantiomeric excess (ee)

Specific Rotation & Enantiomeric Excess

100

Mole Percentage (%)

15

[](R) = +13.6
racemic
mixture

10

80

60

40

-5

20

-10

-15

R S
%ee =
100%
R+S

[]25
D =

Specific Rotation ( mL/g dm)

120

R enantiomer
S enantiomer
[]

%ee(R)
[]25
D (R)
100%

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