Chirality and

Stereogenic Centers

What is chirality?

?The word "chirality" refers to the property of "handness". You right and left hands are very similar, yet
they are not identical. They are related to each other as mirror images, and as such they can not be
superimposed on top of each other. Molecules can also be chiral if they contain one or more chiral
centers.

What is chiral centre?

For the purposes of introductory organic chemistry, a chiral center can be defined as an sp3 hybridized
carbon which is bonded to four different groups. A more contemporary term for "chiral center" (or
chiral carbon) is stereogenic center (or stereocenter), and the terms will be used interchangeably. i.e.If
all the four bonds of carbon are satisfied by four different atoms / groups, it is chiral. Here it should be
noted that isotopes are regarded as different atoms?groups chiral carbon is designated by an asterisk
(*).

Chirality, resulting from the presence of four different groups around a carbon results from an
asymmetry in the molecule. This can be seen by examining the molecules shown below; when
two identical groups are on one carbon, there is an internal mirror plane passing through the
molecule; when four groups are present, there is no internal mirror plane (no symmetry) and
hence the carbon is chiral.

Refer to this video for chirality:-

Optical isomerism in 2-bromobutane:

The carbon which is bound to the bromine (carbon #2) is a stereogenic center; it is sp3
hybridized and it is bonded to four different groups i.e.

a hydrogen atom, a bromine atom, a

methyl group and an ethyl group.

All of the other carbons in this molecule are not stereogenic centers, since they are all bonded to
at least two hydrogens.
2-Chloro-3-bromobutane has two stereogenic centers:
Carbon

#2

in

this

molecule

is sp3 hybridized

and

is

attached

to

four

different

groups i.e. a hydrogen atom, a chlorine atom. a methyl group and a CHBrCH3 group.
Likewise, carbon #3 is also sp3 hybridized and is attached to four different groups:
a hydrogen atom , a bromine atom, a methyl group, and a -CHClCH3 group.
The remaining carbons are both sp3 hybridized, but each is attached to three hydrogens, and
neither is a stereogenic center.

Optical isomerism in bromochloroiodomethane:

The structural formula of bromochloroiodomethane is

The molecule has one chiral carbon as designated by star. So molecule is chiral. It is non superimposable on its mirror image.

According to Van't Hoff rule,

Total number of optical isomers should be = 2 n; when n is number of chiral centre

The Fischer projections of the two isomers are

Non-super imposable

Can rotate PPL

Optically active

Stereoisomers which are mirror - image of each other are called enantiomers or
enantiomorphs. (i) and (ii) are enantiomers. All the physical and chemical
properties of enantiomers are same except two:
1.

They rotate PPL to the same extent but in opposite direction. One which rotates PPL in
clockwise direction is called dextro-rotatory (dextro is Latin word meaning thereby right) and is
designated by d or (+). One which rotates PPL in anti-clockwise direction is called laevo
rotatory (means towards left) and designated by l or ().

2.

they react with optically active compounds with different rates.

Enantiomers, Diastereomers & Meso Compounds

If an organic molecule contains more than one chiral carbons then the molecule may be chiral or
achiral depending whether it has element of symmetry or not.
Elements of symmetry: If a molecule have either
a) a plane of symmetry, and / or
b) centre of symmetry, and / or
c) n-fold alternating axis of symmetry
If an object is superimposable on its mirror image; it cannot rotate PPL and hence optically
inactive. If an object can be cut exactly into two equal halves so that half of its become mirror
image of other half., it has plane of symmetry.

Centre of symmetry: It is a point inside a molecule from which on travelling equal distance in
opposite directions one takes equal time

Thus, if an organic molecule contains more than one chiral carbons but also have any elements
of symmetry, it is superimposable on its mirror - image, cannot rotate PPL and optically inactive.
If the molecule have more than one chiral centres but not have any element of symmetry, it must
be chiral.

What are enantiomers?

Stereoisomers which are related to each other as mirror images are called enantiomers.
Enantiomers can contain any number of stereogenic centers, as long as each center is the exact
mirror image of the corresponding center in the other molecule.

If one or more of these centers differs in configuration, the two molecules are no longer mirror
images, but are totally different chemical compounds with differing physical and biological
properties. Stereoisomers which are not enantiomers are called diastereomers.

For a molecule with multiple chiral centers, the number of possible diastereomers is given
by Van't

Hoff

rule : x

2n

Where x is the number of possible isomers and n is the number of stereogenic centers. Thus, for
molecules with two stereogenic centers there are four possible stereoisomers. For cholesterol,
with

eight

stereogenic

centers,

there

are

256

possible

stereoisomers,

etc.

A third type of stereoisomer which must be considered is a meso compound. A meso compound
contains at least two stereogenic centers, yet the molecule itself is not chiral. This is because
meso compounds contain an internal plane of symmetry; the molecule can be split by an
imaginary mirror so that all atoms on one side of the mirror are the exact reflection of the atoms
on the other side. This can be seen below for cis-1,2-dimethylcyclopentane; there are two chiral
centers in the molecule since the two carbons labeled with the red asterisk are each bonded to
four different groups. A mirror placed through the molecule, along the plane indicated by the
dashed line, will exactly bisect the molecule with all groups exactly reflected by their counterparts
on the other side of the "mirror".

Stereoisomerism in 2,3-dibromopentane?

The structural formula of 2,3-dibromopentane is

The molecule contains two chiral carbons and hence according to Van't Hoff rule the total
number of optical isomers should be 2n = 22 = 4 and it is. The four optical isomers are.

I,II,III and IV are four stereoisomers of 2,3-dibromopentane.

I and III are enantiomers.
III and IV are also enantiomers
What is relation between I and III; or I and IV; or II and III; or II and IV?
All these pairs are diastereomers, stereoisomers which are not mirror - image of each other are
called diastereomers.
Therefore,
I and III are diastereomers
I and IV are diastereomers
II and III are diastereomers
II and IV are diastereomers

Stereoisomerism in Tartaric Acid

The IUPAC name of tartaric acid is 2,3 - dihydroxy butandioic acid. The structural formula is
HOOC-*CHOH-*CHOH-COOH
The molecule contains two chiral carbon and the number of optical isomers should be 2 n=22=4;
but number of optical isomers reduces to 3 because one molecule has plane of symmetry.

III and IV are same

Rotation of IV by 180 yield III.
I and II are enantiomers

III is meso-form of tartaric acid.

A meso compound is one which is optically inactive although have more than one chiral carbons.
Number of Optical Isomers
Number of possible optical isomers in compounds containing different no. of asymmetric atoms.
1.

The molecule has no symmetry

The no. of d and l forms a = 2n
n

= no. of asymetric atoms

The no. of meso l- forms m = 0

Total no. of optical isomers = a + m = 2n
2.

The molecule has symmetry

The no. of

d and l forms a = 2n -1

Meso forms m = 2n1

Total = a + m
It is add a = 2n1 , m = 2(n-1)/2

Difference between racemic mixture and meso compound

A racemic mixture contains equimolar amounts of enantiomers. It is optically inactive due to

external compensation. It can be resolved into optically active forms. A meso compound is
optically inactive due to internal compensation.
Optically active compounds having no chiral carbon
The presence of chiral carbon is neither a necessary nor a sufficient condition for optical activity,
since optical activity may be present in molecules with no chiral atom and since molecules with
two or more chiral carbon atoms are superimposable on their mirror images and hence inactive.
i)

Any molecule containing an atom that has four bonds pointing to the corners of a tetrahedron will

be optically active if the four groups are different.

ii)

Atoms with pyramidal bonding might be expected to give rise to

optical activity if the atom is connected to three different groups,

since the unshared pair of electron is analogous to a fourth group.

Many attempts have been made to resolve such compounds, but until
recently

all

failed

because

of

umbrella

effect,

also

called

pyramidal inversion. The umbrella effect is rapid oscillation of the

unshared pair form one side of XYZ plane to the other.
iii)

Biphenyls, containing four large groups in the ortho position

so that there is restricted rotation, are optically active if the

rings are asymmetrical.

If either or both rings are symmetrical, the molecule has

plane of symmetry and optically inactive.

Allenes, with even number of cumulative double bonds are optically

active if both sides are dissymmetric.

Specific Rotation
The specific rotation [ ] is an inherent physical property of an enantiomer, which varies with the
solvent used, temp (in C) and wavelength of the light used. It is calculated from the observed
rotation a as follows.
[ ]

Where l = length of tube in decimeters (dm)

C = Concentration in gram cm3, for a solution density in gcm3, for a pure luqid