Chirality

• “Handedness”: right glove doesn’t fit the

left hand.
• Mirror-image object is different from the
original object. =>
 Mirror Planes of Symmetry
• If two groups are the
same, carbon is
achiral.
• A molecule with an
internal mirror plane
cannot be chiral.*

Caution! If there is no plane of symmetry,

molecule may be chiral or achiral. See if
mirror image can be superimposed. =>
 mirror

Cl Cl Are these two

H H structures identical?
 Cl Cl
H H
 enantiomers

Stereoisomers that
are nonidentical
mirror images are
called enantiomers.
diasteriomers CH3 CH3 CH3 CH3

H H H H
cis
Stereoisomers that are
not mirror images are H CH3
called diastereomers.
CH3 H
trans
 Diastereomers
• Stereoisomers that are not mirror images.
• Geometric isomers (cis-trans)
• Molecules with 2 or more chiral carbons.
=>
 Chirality

A molecule is chiral if its two mirror image forms

are not superposable upon one another.

A molecule is achiral if its two mirror image forms

are superposable.
 Bromochlorofluoromethane is chiral

Cl
It cannot be
Br
superposed point
H for point on its
mirror image.
F
 Bromochlorofluoromethane is chiral

Cl Cl
Br Br
H H

F F
To show
nonsuperposability,
rotate this model 180°
around a vertical axis.
 Bromochlorofluoromethane is chiral

Cl Br
Br Cl
H H

F F
Another look
 Enantiomers

nonsuperposable mirror images are

called enantiomers

and

are enantiomers with respect to each other

Chlorodifluoromethane
is achiral
Chlorodifluoromethane
is achiral

The two
structures are
mirror images,
but are not
enantiomers,
because they
can be
superposed on
each other.
The Stereogenic Center
 The Stereogenic Center

a carbon atom with four

w different groups attached to it

x C y also called:
chiral center
z
asymmetric center
stereocenter
 Chirality and stereogenic centers

A molecule with a single stereogenic

center is chiral.

Bromochlorofluoromethane is an example.

Cl C F

Br
 Chirality and stereogenic centers

A molecule with a single stereogenic

center is chiral.

2-Butanol is another example.

CH3 C CH2CH3

OH
Examples of molecules with 1 stereogenic center

CH3

CH3CH2CH2 C CH2CH2CH2CH3

CH2CH3

a chiral alkane
A molecule with a single stereogenic center
must be chiral.

But, a molecule with two or more

stereogenic centers may be chiral
or it may not
Symmetry in Achiral
Structures
Symmetry tests for achiral structures

Any molecule with a plane of symmetry

or a center of symmetry must be achiral.
 Plane of symmetry

A plane of symmetry bisects a molecule into two

mirror image halves. Chlorodifluoromethane
has a plane of symmetry.
 Plane of symmetry

A plane of symmetry bisects a molecule into two

mirror image halves. Chlorodifluoromethane
has a plane of symmetry.
A molecule with a plane of symmetry
cannot be chiral
• Example
– 2-Chloropropane (a) has a plane of symmetry but 2-
chlorobutane (b) does not
Locating a Stereocenter (Chiral Carbon)

*
CH3 CH C OH

OH
Lactic acid
 Locating a Stereocenter

Br

CH3 CH2 CH2 CH2 CH2 C* CH2 CH2 CH2 CH3

H
Locating a Stereocenter
O

CH3
*
H
Locating a Stereocenter
H CH3
no stereocenter
The Cahn Ingold Prelog
R-S Notational System
 Assign (R) or (S)
• Assign a priority number to each group attached to the
chiral carbon.
• Atom with highest atomic number assigned the highest
priority #1
• Working in 3D, rotate molecule so that lowest priority
group is in back.
• Draw an arrow from highest to lowest priority group.
• Clockwise = (R), Counterclockwise = (S)
If the order of decreasing precedence traces a
clockwise path, the absolute configuration is R. If the
path is anticlockwise, the configuration is S.

d d

a b b a

c c

Order of decreasing rank:

a>b>c >d
clockwise anticlockwise
R S
 Enantiomers of 2-butanol

H H
CH3CH2 CH2CH3
C OH HO C

H3C CH3

(S)-2-Butanol (R)-2-Butanol
 The Cahn-Ingold-Prelog Rules

Orient the molecule so that lowest-ranked (lightest)

substituent points away from you. Trace the path from
highest to lowest. Clockwise (R), Counter Clockwise (S)
 Enantiomers of 2-butanol

H H
CH3CH2 CH2CH3
C OH HO C

H3C CH3

(S)-2-Butanol (R)-2-Butanol
 Stereogenic center in a ring
R or S ?

H3C H

R
H

—CH2C=C > —CH2CH2 > —CH3 > —H

Groups with double or triple bonds are assigned
priorities as if their atoms were duplicated or
triplicated

Vinyl vs isopropyl
 – Problem: Are A and B identical or enantiomers?
– Name them using R- S- designation

(R)-1-bromo-1chloroethane

http://www.cem.msu.edu/~reusch/VirtualText/sterism3.htm