STEREOCHEMISTRY

Study of arrangement of different groups or atoms in a molecule in space is termed

stereochemistry. It deals with the chemical and biological consequences of the arrangement
of atoms in space. It deals with the study of molecules as three dimensional objects.

ISOMERISM: Study of compounds having same molecular formula but different structural
and physical/chemical properties.

ISOMERISM

TAUTOMERISM
STEREO
ISOMERISM
STRUCTURAL
ISOMERISM
CHAIN
ISOMERISM

POSITION CONFORMATIONAL
ISOMERISM

FUNCTIONAL
GROUP
ISOMERISM CONFIGURATIONL

METAMERISM

OPTICAL

OPTICAL

STRUCTURAL OR CONSTITUTIONAL ISOMERISM: Isomers differ in connectivity of atoms

including bond multiplicity: disregarding configuration. The atoms are arranged in completely
different order. Molecular formula remains same but structures may vary due to branching,
shift of functional groups, distribution of atoms etc.

CHAIN ISOMERISM

Chain isomerism arises due to the difference in arrangement of C atoms in the chain. These
isomers arise because of the possibility of branching in carbon chains, e.g., there are two
isomers of butane, in one of them, and the C atoms lie in the straight chain where as in the
other chain they are branched.
 1
Few more examples are given below.

1.

1-Butene 2-Butene 2-Methyl-1-propene

I and II are not chain isomer because same number of C atoms are there in the main chain.

(Ring Chain Isomerism: Compounds having same molecular formula but possessing open
chain and cyclic structures-------------- I and IV/V)

2.

n-Pentane 2Methylbutane 2,2-Dimethylpropane

 2
3.

1-Butanol 2-Butanol 2-Methylpropanol

POSITION ISOMERISM

In position isomerism, the basic carbon skeleton remains unchanged, but important groups
are moved around on that skeleton. These isomers have same molecular formula but differ
in the position of functional group/multiple bond/substituent keeping no change on the main
chain or side chain.

1.

1-Butanol 2-Butanol

Position of hydroxyl groups changed its position in two structures.

2.
 Position of keto group changed its position in two structures.

3
3.

1-Butene 2-Butene Position of double bond changed its position in

two structures.

4.

Position of methyl group changed its position in two structures.

METAMERISM:

This type of isomerism arises due to the presence of different alkyl chains on each side of
the functional group. It is a rare type of isomerism and is generally limited to molecules that
contain a divalent atom (such as sulfur or oxygen) surrounded by alkyl groups.
 4

TAUTOMERISM:

It arises due to 1,3 migration of H atom from one polyvalent atom to the other within
the same molecule. Isomers are known as tautomers which are in equilibrium. Tautomerism
is a dynamic equilibrium between two compounds with same molecular formula. A tautomer
of a compound refers to the isomer of the compound which only differs in the position of
protons and electrons. Typically, the tautomers of a compound exist together in equilibrium
and easily interchange. It occurs via an intramolecular proton transfer. The most common
form of tautomerism is keto-enol tautomerism. A carbonyl compound containing at least one
α hydrogen atom is converted to an enol by the transfer of a α-hydrogen on to the oxygen
atom.
For example,
 5
Ethyl acetoacetate contains two functional groups, one is keto and another one is ester.
Methylene hydrogens are slightly more acidic in nature than methyl hydrogen. Thus, one of
this methylene hydrogen is moved towards keto functional group and exhibit isomerism
called keto enol tautomerism.

Because of the intramolecular H bonding the six-membered ring formation takes place,
which is stable.

FUNCTIONAL GROUP ISOMERISM:

In this variety of isomerism, the isomers contain different functional groups - that is, they
belong to different families of compounds (different homologous series).

6
TWO DIMENSIONAL REPRESENTATION OF THREE DIMENTIONAL MOLECULES
Kekule described correctly the tetravalent nature of carbon. Chemistry was, however
still viewed in two dimensional ways until 1874. In that year, J. vant Hoff and Le Bel added a
third dimension to carbon. They proposed that, four bonds of carbon are not randomly
oriented but have a specific orientation. vant Hoff (Nobel prize, 1901) further advanced the
idea and proposed that, tetrahedral bonded to four different groups (at the corner of the
regular tetrahedron) sits at its center and represented a chiral molecule.

FLYING-WEDGE OR WEDGE-DASH REPRESENTATION

The flying wedge projection is the most common three dimensional molecules on a
two dimensional surface (paper). This kind of representation is usually done for molecule
containing chiral center. In this representation, the ordinary lines represent bonds in the
plane of paper. A solid wedge represents a bond above the plane of paper and dashed or
broken wedge represents a bond below the plane of the paper.

FISCHER PROJECTION FORMULAE

The C chain is projected vertically, the horizontal bond attached to the C are considered to
be above the plane of the paper and towards the viewer and the vertical bonds are
considered to be below the plane of the paper and at the back of the viewer.

7
∙ In Fischer projection formula, if two like groups are on same side, the molecule is
called erythreo.

∙ If two like groups are on opposite sides is called threo.

Representation of three dimensional molecules is a flat structure. A tetrahedral C is

represented by two crossed lines.
 ∙ Place C chain vertically

∙ Top most position having C bearing functional group

∙ -OH or –NH2 placed horizontally.

SAWHORSE FORMULAE

In this representation, the molecule is viewed slightly from above and from the right and
then projected on paper. The bond between two C atoms is drawn diagonally and of a
relatively greater length for the sake of clarity. The lower left hand C is taken as front C and
the upper right hand C as back C.

∙ All parallel bonds in Sawhorse formula are called eclipsed and all anti parallel bonds
are opposite or trans/anti each other.
The Sawhorse presentation of eclipsed and anti conformation.

8
NEWMAN PROJECTION FORMULAE:

Newman devised a very simple method of projecting the three dimensional formula on
paper which are known as Newman projections.

∙ In this formula, the molecule is viewed from the front. The C atom nearer to the eye is
represented by a point and the three atoms or groups are shown attached to it by
three lines at an angle of 120 º to each other.

∙ In this formula, all parallel bonds are eclipsed and all anti parallel bonds are staggered.

9
STEREOISOMERISM: In stereoisomers, they have same bonding connectivity of their
atoms but different orientation in space. Stereoisomers are of three types. (i) Configurational
(Geometrical), (ii) optical, (iii) conformational.

CONFIGURATIONAL ISOMERS/GEOMETRICAL ISOMERS

Stereoisomers, which arises due to some shot of rigidity within the molecules, and which can
be inter converted only by breaking and remaking of bonds and not by rotation around σ
bond are called configurational isomers.
Stereoisomers, those IUPAC name is same, but spati0al orientation is different. Prefix to be
added in IUPAC name to indicate the spatial orientation of groups or atoms.
CONDITIONS: 1. Restriction in rotation, consider π and σ bond.

2. Restricted atoms have different substituents.

1. Restriction in rotation:
 10

They have same molecular formula but differ in spatial orientation/arrangement of hydrogen
atoms and methyl groups around double bond. Such isomers which have same structural
formula but different spatial arrangement of atoms or groups around double bond are called
geometrical isomers and that phenomenon is known as geometrical isomerism. They have
different properties like dipole moment, heat of combustion, melting and boiling point, heat of
hydrogenation etc.
The isomers in which similar atoms or groups lie on the same side of the double bond is
called “cis” (Zussamen means together that is why Z) and isomers in which the similar atoms
or groups lie on the opposite side of the double bond is called “trans” (entagagen means
opposite that is why E).

For geometrical isomers molecules must have

(i) π bond (we know that, double bond consists of σ and π bonds. Π bond forms by side to
side overlapping of un-hybridized p orbitals which lie above and below σ bond).
(ii) cyclic structure, one or more cycles, if present
 11
(iii) both π bond and cycles

If one of the C atoms tries to rotate, the π cloud breaks which requires energy. Thus rotation
atroom temperature is not possible in case of double bond and triple bond molecules. As a
result many substituted alkenes present in two different forms which differ from each other.

2. Restricted atoms have different substituents.

 12
EXAMPLE

1.

2.

3.
 13
4.

5.

6.
 14
OPTICAL ISOMERS:

Optical isomers are molecules that differ three dimensionally by the placement of
substituents around one or more atoms in the molecules.

Optical isomers were given their name they were first able to be distinguished by how they
rotated plane polarized light. Optical activity is the ability of chiral molecules to rotate the
plane polarized light, measured using a polarimeter. A simple polarimeter consists of light
source, polarizing lens, sample tube and analysing lens.
15
16
The molecules which rotates the plane of plane polarized light is called optically active
moleculeand they are chiral molecule and they can exhibit enantiomeric pair and that exactly
what happened for racemic tartaric acid. Pastur first separated these two crystals of tartaric
acid from their mixture using microscope. The initial argument that was placed to support the
phenomenon of optical activity was based on existence of C that Vant Hoff and La bel told.
According to them, C attached with four different groups and atoms exhibit stereoisomerism
and he named that C as asymmetric center. Later on it was called as chiral center.

CHIRAL MOLECULES:

The term steroecenter is also used, but it is a broader term. Chirality centres are
however, not limited to C, enantiomers are known with compounds having stereocenters
other than C i.e., tetrahedral, P, N, etc.
Initially it was proposed that, the most common cause of optical activity in organic
molecules is a tetrahedral atom (generally C) bonded to four different groups. Thus
existence of chiral centre is important for a molecule to show optical activity.
But the problem started when it was shown that there is a molecule which was called
mesotartaric acid. The earlier argument that, a molecule must have a C with four different
groups which is chiral centre does not hold when the number of chiral centre increases. In
compound there are two chiral centres which are marked. According to the earlier argument,
the existence of this type of C is mandatory to show optical activity does not hold good. So
there is a problem in saying that, optical activity arises due to presence of chiral centre in a
molecule. Then it was revised the definition or reason for molecule to show optical activity.

17

Initially it was said that, there must be chiral centre. Then it was revised that, there are
molecule which can access chiral centres be optically inactive, especially for molecules when
the chiral centres are similar in nature, i.e., same set of four groups are attached to the C.
Thus, presences of chiral centres are required but some molecules are there, where in spite
of having chiral centre molecules may be optically inactive.
Sometimes, molecules having no chiral centre are optically active—like allen

system.

Thus, first we said, there must be chiral centre in a molecule, then it was modified a little bit
that, there are some molecules whose chiral centre are similar and this may destroy the
optical activity. There are some molecules where there is no such chiral centre but the
molecules show optical activity.
Thus there must be something wrong in this concept. Scientists again look back to
the entire molecules and they found where actually the argument is going wrong. The
argument is going wrong because it is based on the presence of the chiral centre, which is
not a mandatory condition for a molecule to be optically active. The chiral centres actually
bring stereoisomerism in the molecule. When this type of centres are present you can
generate stereoisomers, however this is not directly connected to the optical activity of the
molecules.

Optical activity or chirality is based on what is called symmetry concept. Chirality is

the most sufficient condition to show optical activity. A molecule which does not have plane
of symmetry and centre of symmetry must be optically active. If any of the symmetry
elements is present, the molecule is optically inactive. Example is lactic acid and tartaric
acid. Now optical activity is based on what is called symmetry concept.
A carbon atom with four different groups bonded to it lacks the two key symmetry elements,
plane of symmetry and centre of symmetry (as well as a rotational axis of symmetry and is
called an asymmetric centre of alternatively a chirality centre.

18

THE TERM ACHIRAL:

Objects and molecules which are superimposable on their mirror images e.g. figures given
below are achiral. An internal plane of symmetry is a hypothetical plane which bisects an
object or a molecule into mirror reflective halves. An object or a molecule with an internal
plane of symmetry is achiral (can be superimposed on its mirror image). Thus, given shapes
are achiralsince it can be divided into two equal halves by its plane of symmetry. Similarly, for
molecules,we have to inspect that what is the symmetric properties of this molecules. These
symmetric properties actually dictate the presence or absence of optical activity of some
molecule as in the case of meso tartaric acid, which contains a plane of symmetry. A hand is
chiral since a plane cannot split it into two equal halves. Similarly, either of the (+) or (-)
enantiomers of tartaric acid is chiral.

Likewise, there are three symmetry elements and in total there are four symmetry elements
possible in a molecule.
Nonsuperimposability of a structure on its mirror image: The ultimate criterion for
chirality i.e., existence of enantiomers in a molecule is the nonsuperimposability of a
structure and its mirror image. (Thus enantiomers must be isomers and mirror images as
well, i.e., they must not be superimposable).

19
Elements of symmetry and chirality: An alternative approach to decide if or not a
structure is chiral i.e., capable of existing in enantiomeric forms (optically active forms) is to
examine the symmetry of a molecule.

SIMPLE AXIS OR PROPER AXIS OF SYMMETRY (Cn):

The first symmetry element that one should consider is what is called simple axis or proper
axis of symmetry (Cn). The subscript denotes the fold of axis. It means that, if you have a
molecule and if you rotate it along an axis.

It is imaginary axis by which if you rotate the molecules by certain angle which will gives you
the identical structure with the original one then your molecules possess simple axis of
symmetry. In the given figure, it happens by rotation of 180º not by rotation of 90º. “n” is
basically how much you have rotated the molecule to obtain the molecule which has similar
appearance, (360 / that angle), that is required to rotate the molecule around the axis to
appear the same like original one. In this case we are rotating by 180 º, so the fold this has
got a simple axis of symmetry. Because we come to the same appeared molecule after
rotation of 180 º, i.e., before we reached the 360 º because if any one rotate a molecule by
360 º
that always remains the same. Before 360 º if you find an angle where it appears the same,
the minimum rotation that is required and (360/that angle) will gives you fold. In the above
case fold = 2 means the molecule has 2-fold simple axis of symmetry.
A molecule can have multiple sets C axis. A molecule may have C2, C3 axis within
the same molecule.
PLANE OF SYMMETRY (σ):

It is an imaginary plane which divide the molecules by two halves in such way that, one half
is the mirror image of another half. Here, one half is not identical with the other half, it should
be mirror image of another half.

A molecule may have multiple planes of symmetry. It is not the case that, a molecule
has only one plane of symmetry. There are molecules which have got one plane of
symmetry. There are molecules which have multiple planes of symmetry like the given
molecule as we have identified as plane of symmetry. The plane of symmetry is designated
as σ (σ plane).

20

The molecule may have multiple planes of symmetry. It is not the case that, a molecule has
only one plane of symmetry. There are molecules which do not have any plane of symmetry.
There are molecules which have multiple planes of symmetry. If you bisect the given
molecules by these way one part is the mirror image of other part. This plane of symmetry is
designated as σ (σ plane).
All planer molecules posses atleast one plane of symmetry, identical with molecular
plane. Linear molecules have infinite number of σ planes which intersects C∞. The planes of
symmetry which are perpendicular to the principal axis are termed σh (h for horizontal)
whereas those containing the principal axis are marked σv (v for vertical). Plane bisects the
angle between a pair of rotational axis C2, we have a diagonal mirror plane σd

CENTRE OF SYMMETRY (INVERSION CENTRE / i):

A molecule is said to have centre of symmetry or an inversion centre if all straight line that
can be drawn though the centre of the molecule meet identical atoms (or points) at the same
distance from the centre. In other words, inversion of all atoms (or points) in the molecule
through the points leads to an arrangement indistinguishable to the original. There can be
one such inversion centre in the molecule. Thus, it has to be1, either it is present or not
present.

21

If you take central point of the molecule, and if you join Br to this point and extend the line
backward to an equal distance you reach the same atom (Br here). Same thing happens
with H. Thus, centre of symmetry is the central point in the molecule and the line joining that
substituent and if you extend it backwards, you find an identical group at identical distance.
It has to be true for all the atoms present in the molecule.
In the above molecule centre of symmetry is not present.

ALTERNATING AXIS OF SYMMETRY (ROTATION REFLECTION AXIS / Sn):

A molecule has an n-fold alternating axis of symmetry (Sn) if the molecule when
turned 360º/n about an axis followed by reflection in a plane perpendicular to that axis
brings the molecule in a position indistinguishable from the original.

It turns out that, S1 is the same as plane of symmetry (σ). S2 is same as centre of
symmetry (i) and higher descriptor of Sn are rare. Thus, 1,3 dichloro 2, 4 dibromo
cyclobutane has a centre of symmetry as its only symmetry elements. When it rotated 180 º
about the axis

22
passing through the centre of the molecule and then reflected in a mirror perpendicular to
this axis, an arrangement superimposable on the original is obtained. The multiplicity i.e.,
foldedness of the alternating axis is given by the extent of rotation in the 1st step i.e., 360º
/180º = 2, thus it has 2-fold axis (S2).

Now, what we need to do? We have rotate the molecule by 180º around an axis, we
have taken a mirror image of that rotated molecule, the mirror should be placed
perpendicular to the axis, then it was observed that, mirror image should be identical with
the original molecule. This molecule has got 2-fold alternating axis of symmetry.
A plane of symmetry is equivalent to a one fold alternating axis of symmetry (S1). Some
molecules have symmetry planes in addition to simple axis of symmetry others have a
symmetry plane as their sole symmetry elements. Water has two mutually perpendicular σ-

23
planes both containing the C2 axis and intersecting along it. All planer molecules like water,
must contain at least one symmetry plane which is the molecular plane.

For detecting an alternating axis of symmetry for the given molecule, we have rotate the
molecule by 90º around an axis, we have taken a mirror image of that rotated molecule, the
mirror should be placed perpendicular to the axis, then it was observed that, mirror image
should be identical with the original molecule. This molecule has got 4-fold alternating axis
of symmetry.
H2O:
 24
NH3

CHCl3
BENZENE:

25

HCHO:

C2H4:

In the sawhorse projection drawn in the eclipsed form (plane of symmetry clearly visible) C3
is rotated to get staggered form where now centre of symmetry is also clearly seen.
 26

Presence of S2 axis in meso tartaric acid (drawn as sawhorse staggered conformation).

An achiral molecule is identical and can be superimposed upon its mirror image, whereas a
chiral molecule is one which cannot be superimposed on its mirror image. The property of
chirality can thus be described by constructing the models of two molecules under study and
look for the existence of non-superimposable mirror image. One may describe the chirality in
terms of symmetry elements of the molecule under study. When the molecule has a centre
of symmetry (i), plane of symmetry (σ) or alternating axis of symmetry (Sn) the mirror images
of the molecules are superimposable and the molecule is achiral.
It is not necessary condition for chirality that a molecule should have no symmetry
elements. A necessary and sufficient condition for a molecule to have a non-superimposable
mirror image that it must not contain a plane. A centre or a n-fold alternating axis of
symmetry. However, these requirements do not preclude the presence of a simple axis of
symmetry in the chiral molecule. There are several examples of such molecules with
non-superimposable mirror images (chiral compounds) in which symmetry elements is
detected (C2). The allenes provide yet another example of chiral molecules with C2 axis.

THE TERMS CHIRAL, ASYMMETRIC AND DISSYMETRIC:

One uses three terms (chiral, asymmetric and dissymmetric) for molecules which show
enantiomerism (optical isomerism i.e., chirality). An asymmetric compound (chiral) is that,
which lacks all elements of symmetry but have C1 symmetry. All molecules contain an infinite
number of C1 axis i.e., if one rotates anything 360º (360º/1)=360º passing through it in any
direction, the result is the same arrangement in the same three dimensional orientation
which it had originally. A compound which has single C atom and has four different groups
around it is always asymmetric (lactic acid, bromochlorofluoromethane). The term chiral is
synonymous with dissymmetric. When the chiral compound has a simple axis of symmetry
(Usually a C2 axis) and no other symmetry elements is present in the compound is then
termed as dissymmetric.

Tartaric acid (drawn in the eclipsed form) may be taken as yet another example to study its
chirality in terms of symmetry elements. This acid exists as a pair of enantiomers each of
which is diastereomeric with the meso form.

27

One can easily detect C2 axis. Rotation of (+) tartaric acid through the axis by 180º gives the
original, to show that (+) tartaric acid has a simple two-fold axis of symmetry C2.

CONFIGURATION AND THEIR SPECIFICATIONS D-L AND R-S SYSTEM:

The configuration of a stereocentre is the specification of the relative spatial arrangement of
 the four groups attached to it. Absolute configuration specifies their order so

28
as to distinguish the two enantiomers and there by define their chirality i.e., the specification
of (R) or (S) at each stereocentres in a molecule.

The former DL system to denote absolute configuration is not without faults and
therefore, the system is seldom used today except of some classes of compounds like
carbohydrates and amino acids. The (+) enantiomer of glyceraldehyde has its OH group on
its right of the Fischer projection (D-configuration) while the (-) enantiomer of glyceraldehyde
has its OH group on its left of the Fischer projection (L-configuration).

D-series of sugars are those with the OH group on the highest numbered stereocenters (i.e.,
the bottom stereocenters) on the right of the Fischer projection and L series have it on left. D
and L configurations are not related to the optical rotations of the sugar to which they
applied. Some sugars are D-(+) while others are D-(-), thus D # d and L # l. D-(+) glucose
means dextrorotatory glucose has the same absolute configuration at the highest numbered
stereocenters as that of D-glyceraldehyde (OH group on the bottom stereocenters on the
right in Fischer projection).
 29
The R and S Designations from perspective formulae---Three dimensional drawing:

The system now widely used in the Cahn-Ingold-Prelog (R-S) system (which relates all
compounds only one set of rules) in which four groups attached to the stereocenter are
numbered 1, 2, 3 and 4 and are ranked according to a set of sequence rules so that they
can be assigned priorities of arrangement in a sequence 1 > 2 > 3 > 4. In a simple case the
priorities follow standard sub rules.

SEQUENCE RULES OR STANDARD SUBRULES

1. Higher atomic number precedes lower, e.g., Br > Cl > S> F > O > N > C >
H 2. Higher atomic mass number precedes lower, e.g., T > D > H
3. Cis precedes trans, Z precedes E.
 30
(a) Atoms directly attached to the central chiral atom must be sequenced first according to
standard sub-rule 1. If the priority remains undecided for some of the groups, one passes
over to the next atom to the groups and the exploration continues until a decision is reached
on the basis of sub-rule.

-CH2CH2CH3 > -CD2CH3 because propyl > ethyl but –CH2CD2CH3 > -CH2CH2CH3

(b) In case a group bifurcates, one must proceed along the brunch providing the highest
precedence until a difference is encountered. The decision must be made at the earliest
opportunity and once made, cannot be changed from the consideration of substituents
further along the chain.
 31
(c) When the central atom is a part of ring system, each branch is followed until decision is

reached.

(d) In case of atoms with multiple linkages, the atom to which they are multiply bonded must
be duplicated or triplicated as the case may be at the both ends of multiple bonds. The
duplicateatoms are placed into parenthesis and except of hydrogen are made up to ligancy
four with phantom atoms of atomic number zero.
 32

ATOMS OR GROUPS WITH INCREASING PRIORITY:

R-S NOMENCLATURE IN FLYING WEDGE:

1. We have to identify the stereocenters, where number of two groups attached to it is

not identical.

2. Arrange the groups or atoms according to their priority and rank them.
3. Draw line from 1st priority group to 2nd priority group to 3rd priority group.

4. When #4 group is in the back side of the plane, clockwise rotation gives “R” and anti
clockwise rotation gives “S” configuration.
 5. When #4 group, is up side of the plane, clockwise rotation gives “S” and anti
clockwise rotation gives “R” configuration.

33

6. A three dimensional model of the isomer to be designated is viewed from the side
opposite the group of lowest priority (four back rule). The priority sequence 1 to 2 to 3
(decreasing priority) of the remaining three groups is determined and if it as found
clockwise, the symbol, “R” is used to designate the configuration and if the sequence is
counter clockwise the symbol “S” is used. “R” and “S” are from Latin words rectus and
sinister meaning right and left.

When the lowest priority group is oriented towards one’s eye, one may imagine holding the
molecule by the group at the top and rotating it so that the group of lowest priority is
positioned away and can be viewed through the stereogenic centre.
When the group of lowest priority is drawn at the top, one can look along the C-H bond from
below the orientation. Alternatively, one can tilt the orientation so that it can be viewed
conveniently for the assignment of configuration.

34

When the lowest priority group is towards one’s eyes one may adopt alternative option.
Interchange the position of any two groups twice at stereocenter retains its configuration and
also puts groups of lowest priority away from the viewer.

PROJECTION:

1. Identify the stereocenters.

R-S NOMENCLATURE IN FISCHER

2. Determine priorities. Draw line from 1st priority group to 2nd priority group to 3rd priority
group.

3. Lowest priority group if present in horizontal position (above the plane) clockwise
rotation gives “S” and anti-clockwise rotation gives “R” configuration.
4. Lowest priority group if present in vertical position (below the plane) clockwise rotation
gives “R” and anti-clockwise rotation gives “S” configuration.

35
NUMBER OF POSSIBLE STEREOISOMERS:

In many organic compounds, there is more than one stereocenters and such a compound can
have a maximum of 2n stereoisomers where n is equal to number of stereocenters.
ENANTIOMERS: Stereoisomers which have non-superimposable mirror image relationship.
DIASTEREOMERS: Stereoisomers which have non-superimposable non mirror image of each
other.
In the given aldotetrose, C4H8O4, has two stereocenters and can exist in four stereoisomeric
form as two pair of enantiomer.
 36
Here, in the above case neither erythroses bears a mirror image relationship to either of the
threoses, which are therefore, diastereomers (threoses and erythreoses are diastereomers).
Unlike enantiomers, which have similar physical and chemical properties (achiral
atmosphere), diastereomers different physical and chemical properties.

In aldohexoses have four stereocenters and a total 24 = 16 stereoisomers

possible.
 37
ASSIGN CONFIGURATION TO THE COMPOUNDS:

CONFORMATIONS AND STEREOISOMERISM OF ACYCLIC SYSTEM:

Conformation and configuration: Stereoisomers separated by high energy barrier (>100

kJmol-1) are isolable at room temperature and are called configurational isomers.
Stereoisomers separated by relatively low energy barrier (<60KJ mol-1) are easily
interconvertible at ambient temperature and are called conformational isomers or
conformers. Unless a conformation is held rigid by a small ring or double bonds, a molecule
have an infinite number of conformations, but only one configuration.
Dihedral Angle: The dihedral angle is an important stereochemical parameter, much more
than bond length and bond angle which are structural parameters. When ethane molecule
rotates about C-C bond, two extreme conformations can results: the staggered conformation
and eclipsed conformation. An infinite number of conformations between these two extreme
are also possible. The potential energy relationship between conformations is conveniently
discussed in terms of dihedral angle. A dihedral angle (θ), is the angle generated by two
intersecting planes.
 38
Two of the remarkable conformations of ethane are eclipsed and staggered conformation.
The staggered conformation of ethane is the low energy form while the eclipsed
conformations represent transition state. The energy difference between the conformers,
which in fact represents the barrier of interconversion between two staggered conformers, is
about 3 kcal/mol (12 kJ/mol). Thus in an alkane in general, each pair of eclipsed bond that it
contains leads to an energy cost of about 1 kcal/mol (4.2 kJ/mol). This torsional strain is
primarily due to electron pair repulsions when bonds are eclipsed. The activation energy for
rotation about C-C bonds in ethane is small, the thermal energy from the surroundings at the
room temperature (20 kcal/mol, 83.7kJ/mol) is sufficient to cause staggered conformations of
ethane to interconvert millions of times each second at room temperature. Thus the internal
rotation though not completely free but represents a rapid process. The barrier of rotations
about most single bonds is in the range (3-5 kcal/mol, 12-21 kJ /mol) to allow fast rotations
about most single bonds at room temperature.
 39
For a compound of the type A-CH2-CH2-B (1,2 disubstituted ethane) e.g., n-butane there are
four extremes, (i) a fully eclipsed conformation (syn-periplanar) and (ii) partly eclipsed
conformation (anticlinical), (iii) fully staggered conformation (antiperiplanar) and (iv) another
staggered conformation (gauche or syn-clinical). In ethane all the staggered conformations
are equivalent, in n-butane on the other hand there are two different staggered
conformations. In one of these (synclinal) there is a gauche relationship between methyl
groups while in other conformation the relationship is anti (antiperiplaner). Two groups are
said to be gauche when the dihedral angle between them is 60º and in anti-conformation,
the groups are in maximum distance apart, the dihedral angle between them being 180º.
These staggered conformations are free from torsional strain. However; the antiperiplaner
conformer is the most stable, because the methyl groups are far apart. The methyl groups in
gauche conformations are close enough to reach other, so that the van der Waals forces
between them are repulsive. This repulsion causes the gauche conformations to have
approximately 0.9 kcal/mol (3.8 kJ/mol) more energy than the anti-conformation. The
eclipsed conformations represent energy maxima in the potential energy diagram. Eclipsed
conformations not only have torsional strain, they have additional van der Waals repulsions
arising from both eclipsed methyl groups and hydrogen atoms or between the eclipsed
methyl groups. While it takes about 3 kcal/mol (12 kJ/mol) for ethane to rotate from
staggered to eclipsed conformations, it takes about 5 kcal/mol (21 kJ/mol) for n-butane to
rotate from anti to synperiplaner conformation.
For butane and most of the molecules of the type A-CH2-CH2-A or A-CH2-CH2-B, the anti
conformation is most stable.

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