BASICS OF STEREOCHEMISTRY

PRESENTED BY- MANISHA

[Link]. PHAMA. CHEM.
HNBGU(CENTRAL UNIVERSITY)
 INTRODUCTION

• Stereochemistry is the branch of chemistry that involves “the study of the different spatial
arrangement of atoms in molecules.
• The structure of a molecule can vary based on the 3d arrangement of the atoms that constitute
it.
• The branch of chemistry is commonly referred to as 3-D chemistry since it focuses on
stereoisomers (chemical compounds with the same molecular formula but different spatial
arrangement in three dimensions).
• One of the branches of stereochemistry deals with the study of molecules that exhibit
chirality,which is a geometric property of molecules that make them non superimposable on
their mirror images.
• Another branch of 3-D chemistry known as dynamic stereochemistry,involves the study of the
effect of different spatial arrangemets of atoms in molecules on the rate of a chemical reaction.
 HOW IMPORTANT IS STEREOCHEMISTRY?
Example 1– starch and cellulose are two polymers that belong to the
family of biomolecules called carbohydrate.

Cellulose and starch are both composed of the same repeating unit.

Starch and cellulose are isomers because they are different

compounds with the same molecular formula(C6H10O5)n

They are stereoisomers because only the three dimensional

arrangement of atoms is different.
 FUNDAMENTAL DIFFERENCE IN
CELLULOSE AND STARCH
• In cellulose the oxygen
atom join two ring using
two equatorial bonds.

• In starch the oxygen

atom join two ring using
one equatorial and and
one axial bond.
 THALIDOMIDE DISASTER

• An example of the significance of stereochemistry can be observed in the thalidomide

disaster that struck Germany in the year 1957.
• The drug thalidomide was sold as an over the counter drug,initially intended to combat
[Link] was used by pregnant women to alleviate morning sickness.
• However it was discovered that the drug underwent racemization and formed a mixture
of enantiomers in the human body due to the process of metabolism.
• One of these enantiomers is believed to cause genetic damage in developing embroys
and lead to birth defect in babies.
• This is based on the data that over 5000 babies were born with deformed limbs shortly
after thalidomide was commercially sold as an over the counter drug.
• This unforeseen effect of the drug led to the imposition of stricter drug regu;ation laws
(only 40% of the babies born with these deformities survived).
• The disaster signifies the importance of stereochemistry.
 THE TWO MAJOR CLASSES OF ISOMERS

constitutional
isomers
• Differ in the way the atoms are
connected to each other.
• Have different IUPAC name.
• Have same or different functional
groups.
• Have different physical properties,so
they are separable by physical
technique such as distillation.
• Have different chemical properties.
 STEREOISOMERS[STEREO=SPACE]

• Differ only in the way atoms are oriented in

space.
• Stereisomers have identical IUPAC names
(except for a prefix like cis or trans).
• Same physical properties because they
differ only in the 3d arrangement of atoms.
• Stereoisomers always have the same
functional groups.
SUBDIVISION OF ISOMERS
 CONFORMATIONAL ISOMERS

• Structure that can be interconverted simply by rotation about sigma

bonds are conformation of the same molecules.

CONFIGURATIONAL ISOMERS
• Structure that can be interconverted only by breaking the bonds have
different configuration and are stereoisomers.
 GEOMETRICAL ISOMERS:

• These isomers result from restricted rotation ,restricted

rotation can be caused by either a cyclic structure or a double
bond.
Conditions of geometrical isomers:
A) GEOMETRICAL ISOMERISM arises due to the presesnce of a
double bond or a ring structure.
 CASE 2

• Different group should be

attached at each doubly
bonded atom.
 3

• Geometrical isomers are also called configurational isomers.

Geometrical isomers are two different compounds.
 Pi bond lock the molecule. And
this, restrict the rotation around
the carbon carbon double bond
or is responsible for the
geometric isomerism in alkene.
 CIS AND TRANS ISOMER

If the two similar groups are on same side of restricted bond (double
bond)the configuration is cis otherwise trans.
Cis and trans isomer can be separate from each other because they are
different compounds with different physical properties for example they
have different boiling point and a different dipole moment.
E,Z NAMING IN GEOMETRICAL
NOMENCLATURE:

E (short for german Entegegen which means

“opposite)

Z(short for german Zusamen which means

“together”)

If the two senior group are on same side of

restricted bond the configuration is Z otherwise E.
 SEQUENCE RULE(CAHN-INGOLD-PRELOG
OR CIP RULE)
For deciding the seniority of groups following (CIP)rules are
applied.
Rule 1– the group with the first group having higher atomic
[Link] senior.
according to this rule the seniority of atom is:
I > Br > Cl > S > F > O > N > C > H
Rule 2- the higher mass isotope is senior:
thus a) T > D > H
Rule 3- if the first group is identical then second atom is
Rule 4- to assign a priority to an atom that is part of
a

multiple bond treat a multiply bonded atom as an

equivalent [Link] singly bonded atom.

 OPTICAL ISOMERISM

• The phenomenon of rotating the plane

polarized light is known as optical activity and
the compound exhibiting this property are
known as optically active compounds.
• In other words, compounds which have similar
chemical and physical properties and differ only
in their optical activity i.e. their behaviour
towards plane polarized light are known as
optical isomers and the phenomenon as optical
isomerism.
 1- plane polarized light: according to physical theory,an
ordinary ray of light vibrates in all plane.

when this light is passed through a nicol prism its vibrations in

all planes, except one are either rejected or absorbed and thus
the emergent beam vibrates only in one [Link] type of
light whose vibrations occur only in a single plane is known as
plane polarized light and the phenomenon is known as
polarization.

when plane polarized light is passed through certain substances

or their solution,or plane of polarization is rotated either towards
right (clockwise) or towards left (anti-clockwise)by a certain
angle.
Such substance which rotate the plane polarized light are
known as optically active and the phenomenon is referred
to as optical activity.

On the basis of the study of optical activity ,the various

organic compounds are divided into three types:

1- dexotro-rotatory (latin dexter=right) d or (+) form

it rotates the plane polarized light to
right.

2- laevo-rotatory( latin laevous=left) l or (-) form

it rotates the plane polarized light to the
left.

3-optically inactive componds : these compounds

don’t rotate the plane polarized light in any direction.
 The magnitude of rotation depends upon the following
factors:
1-nature of the substance.
2-Concentration of the solution.
3-Tempreture of solution.
4-Wavelength of the light used.

2- specific rotation- the measurement of optical activity

is reported in terms of specific rotation which is constant.
Specific rotation as much a characterstics for a particular
compound as its m.P. B.P. Etc.
Formula:
 Optical isomers classified into two types:

1- enantiomers

2- diastereomers

Enantiomers: when two isomers are the non superimposable

mirror image of each other. These are known as enantiomers.

Identical physical properties such as m.P. B.P. , Densities and refractive

indices etc.

Differ only in their action on plane polarized light.

Example: lactic acid

 RECEMIC
MIXTURE:
When two enantiomers are
mixed in equimolar
quantities, it results in the
formation of an optically
inactive compound called
racemic,dl or (+-) form.
Thus if equal amount of d lactic
acid and l lactic acid mixed
together,it will produce optically
inactice or racemic lactic acid.

Recemic mixture has some

physical properties different
from those of the two
enantiomers .
 CHARACTERSTICS OF DIASTEREOMERS

• When the configurational isomers

are not mirror image of each other
these are known as diastereomers
• Different physical properties such as
m.p. b.p. densities ,refractive
indices and specifc rotation.
• It may or may not be optically
active.
 Concept of chirality

• A molecule or object that is not superimposable on its mirror image is said to

be chiral .
• Example left hand and right hand are mirror image of each other but they are
not superimposable.
CHIRALITY :CAUSE OF OPTICAL ACTIVITY

• On studying the structure of several optically active compound it was observed

that most of them contain at least one chiral carbon atom.
chiral carbon: a carbon atom having four different
monovalent atoms or groups is known as chiral carbon or chiral centre.

The term chiral is derived from the Greek word ‘cheir’ means hand.
Similarly the term chirality means handeness in reference to our two hands,
each of which is the non superimposable mirror image of each other.
Thus we can say that the term chiral and chirality are used in reference
to compounds whose mirror image is non superimposable over itself.

1– many but not all molecules that contain chiral centre are
chiral. Example: LACTIC ACID

2- thus there are molecules that although contain chiral centre

yet are achiral .
 3– some chiral molecules do not have any chiral centre
example: 2,3 pentadiene

thus the presence or absence of a chiral centre is no criterion

of chirality thus the presence of achiral centre indicates only
the possibility of chirality in the molecule.