STEREO ISOMERISM

 Isomers are compounds having same molecular formula but different in molecular
structures. Isomers are classified as follows.

 Monosaccharides show isomerism, it has same number of atoms and the same type of
groups in their structures. But they are having different spatial configuration. For
example C6H1206 is the molecular formula for all hexoses. The spatial arrangement of
hydrogen and hydroxyl groups in each of hexoses is different. This phenomenon is called
stereoisomerism or space isomerism and the sugars are called stereoisomers.
 Stereoisomerism is an important character of monosaccharides. Stereoisomers are the
compounds that have the same structural formulae but differ in their spatial
configuration.

 A carbon is said to be asymmetric when it is attached to four different atoms or

groups.

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 The number of possible isomers of any given compound depends upon the number of
asymmetric carbon atoms.
 According to Van’t Hoff’s rule of ‘n’; 2n equals the possible isomers of that compound,
where, n = represents the number of asymmetric carbon
 Monosaccharides containing asymmetric carbon atoms are glucose, fructose, mannose,
galactose and glyceraldehydes
 Glucose contains 4 asymmetric carbons, and thus has 16 isomers.

ENANTIOMERS

 Enantiomers are a special type of stereoisomers that are mirror images of each other.
This is also called as Optical isomerism.
 Optical isomers or enantiomers occur due to the presence of an asymmetric carbon (a
chiral carbon).
 Enantiomers differ from each other in their optical activity.
 Optical activity is the ability to rotate the beam of plane of polarized light either to the
left or to the right.
 When a beam of plane polarized light is passed through a solution exhibiting optical
activity, compounds which rotates polarized light to the right (clockwise direction) is said
to be dextrorotatory and a plus (+) sign is used to designate. Compound which rotates
beam of plane polarized to the left (anticlockwise direction) is said to be levorotatory and
is a minus (-) sign is used to designate.
 These two members present in monosaccharides are designated as D- and L-sugars.
 When equal amounts of dextrorotatory and levorotatory isomers are present, the resulting
mixture has no optical activity since the activities of each isomer cancel the other. Such a
mixture is said to be racemic or a DL mixture.

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 Figure of Plane polarized light and optical rotation.

(a. Plane polarized light rotated in to anticlockwise direction – L form, b. plane polarized
light in to clockwise direction – D form, c. racemate – no overall effect – DL form)

Example:

 The term diastereomers is used to represent the stereoisomers that are not mirror
images of one another.

EPIMERS

 Two sugars which differ from one another only in configuration around a single carbon
atom are termed Epimers.
 For example, glucose and galactose are epimers with respect to carbon 4 (C4-epimers).
That is, they differ in the arrangement of OH group at C4. Glucose and mannose are
epimers with respect to carbon 2 (C2-epimers).
 The interconversion of epimers (e.g. glucose to galactose and vice versa) is known as
epimerization, and a group of enzymes— namely—epimerases catalyse this reaction.
e.g. conversion of galactose to glucose in liver.

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COMPARISION OF ENATIOMER AND EPIMER
Enantiomers
Enantiomers are type of optically active
stereoisomer
They are mirror images of each other
They are non superimposable with each other
Different from each other at every chiral carbon
Physical and chemical properties are same
except in the rotation of planr polarized light
Example: D glucose and L glucose
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Epimers
Epimers are non optical diasterioisomers
They are not mirror images of each other
They are superimposable with each other
Different from each other at only one carbon
atom
Physical and chemical properties are
different from each other
Example: D glucose and D galactose
ANOMERS
  An anomer is a type of diasteroisomer and differs from each other in configuration
at an anomeric or hemiacetal or acetal carbon.
 The hydroxyl group of monosaccharides can react with its own aldehyde or keto
functional group to form hemiacetal and hemiketal. Thus, the aldehyde group of glucose
at C1 reacts with alcohol group at C5 to form two types of cyclic hemiacetals namely α
and β.
 The α and β forms of sugars are called as anomers.
 In glucose, the first carbon atom next to the ring-oxygen is asymmetric and it is called
anomeric carbon.This asymmetric carbon produces two forms of glucoses namely α
glucose and β glucose based on the position of the hydroxyl at the anomeric carbon atom.
 The α D glucopyranose and β D glucopyranose differ in their configuration at the first
carbon atom. This carbon is called as anomeric carbon or acetal or hemiacetal carbon.
 When the hydroxyl group of first carbon attached below the plane of the ring, the
pyranose glucose is called α D glucopyranose. When the hydroxyl group aatched above
the plane of ring the pyranose glucose is called as β D glucopyranose.
 The anomeric carbon is present in first carbon of aldoses and in ketoses it is present in
second carbon.
 Example: α D glucopyranose and β D glucopyranose

COMPARISION OF ANOMER AND EPIMER

ANOMER EPIMER
Anomers are a type of diasterisomers and they Eoimers are a type of diasterisomers and
differ from each other in the configuration of they differe from each other in the
anomeric (or acetal or hemiacetal) carbon configuration at one chiral carbon

Present in cyclic structure Present in cyclic and acylic

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Physical and chemical properties are different Physical and chemical properties are
from each other different from each other

Example: α D glucopyranose and β D Example: D-glucose and D-galactose (C4

glucopyranose (differ in anomeric carbon) epimer)

MUTAROTATION

 Mutarotation means, changing of optical rotation. Tanret explained that when a solution
of freshly prepared crystalline glucose of α-D form is observed in a polariscope, its initial
specific rotation which is + 112° gradually decreases and finally becomes steady at
+52.5°.

 When the solution of pure crystals of β-D glucose is observed in a polariscope, the initial
specific rotation of +19° gradually increases and finally becomes steady at +52.5°.
 The change in rotation is illustrates as +112° +52.5° +19°
(α-D-glucose) (β-D-glucose)

Mechanism of Mutarotation : The αand βanomers of glucose have different optical

rotations. The specific optical rotation of a freshly prepared glucose (α anomer) solution in water
is +112.2° which gradually changes and attains an equilibrium with a constant value of +52.7°.
The optical rotation of β-glucose is +18.7°. Mutarotation is defined as the change in the
specific optical rotation representing the interconversion of αand β forms of D-glucose to
an equilibrium mixture.

The equilibrium mixture contains 63% β-anomer and 36% α-anomer of glucose with 1% open
chain form. In aqueous solution, the β form is more predominant due to its stable conformation.
The αand βforms of glucose are interconvertible which occurs through a linear form.

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