Chapter V:

Stereoisomerism.
 Brainstorming
Before starting today’s lesson, let's review a few
key concepts from our previous chemistry:

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• Definition of Isomerism.

• How can we classify isomerism?

• What the difference between structural

isomerism and stereoisomerism?

• Name one example of structural isomerism

and one example of stereoisomerism.
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 Prof. Fernando González Disla
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Isomerism
 Stereochemistry
• Is the branch of chemistry that studies the three-dimensional arrangement of atoms
and molecules and its effects on their physical, chemical and biological properties.

• Maleic and fumaric acids (cis-trans isomers of butendioic acid) have completely different

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properties despite having the same molecular formula.

Maleic acid (BP = 138°C) is irritating and toxic.

Fumaric acid (BP = 287°C )is an essential metabolite.

• The term stereochemistry was first introduced in 1878 by the German chemist Viktor
Meyer. Its discovery allowed other scientists to propose the tetrahedral shape of the
carbon atom.

Viktor Meyer
 Chirality
• Chirality refers to the property of objects and molecules of not being able to be superimposed
by their mirror images. The word chiral comes from the Greek word “cheir”, which means
“hand”.
• A molecule or object is considered chiral when cannot be superimposed by its mirror image
(because they are not identical). When an object or molecule have a superimposable mirror image,

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it considered achiral or non-chiral. Chirality occurs more frequently in molecules that contain a
carbon atom with 4 different groups attached to it (known also as chiral center or stereocenter).

Cis-1,2-dichloro-cyclopentane
Its non-chiral, because its mirror image its
superimposable over the original.

Compound 1 is chiral because its mirror image Trans-1,2-dichloro-cyclopentane

(compound 2) it's non superimposable and Its chiral, because its mirror image its non-
neither are the products of the rotation. superimposable over the original.
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 Stereoisomerism
Stereoisomers are isomers that have same molecular formula, same sequence of bonding of atoms but
differ in the three-dimensional orientation of atoms in space. Stereoisomerism can be further classified in
diastereomerism and enantiomersim.

a) Diastereomerism: is the type of stereoisomerism where two isomers differ in their configuration and

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are not mirror image of each other. Two types of diastereomers are possible:

1) Cis-trans isomerism: also known as geometrical isomerism, arises because of the restricted rotation
around the carbon-carbon double bond.

2) Conformational isomerism: is the type of diastereomerism where two isomers differ because of the
rotation around the carbon-carbon single bond.

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 Stereoisomerism
b) Enatiomerism: also known as optical isomerism, are isomers that are non-superimposable mirror images of
each other. Enantiomers have identical chemical and physical properties except for their ability to rotate
plane-polarized light by equal amounts but in opposite directions. The isomer which can rotate the plane
polarized light from left to right (clockwise) is known as dextrorotatory and that which can rotate from right
to left (anticlockwise) is known as levorotatory.

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 Polarimetry
• Most physical properties of enantiomers (melting point, boiling point, refractive index, etc.) are
identical. However, they differ in a property called optical activity, in which a sample rotates the
plane of polarization of a polarized light beam passing through.

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• In non-polarized light, electric and magnetic fields randomly orient in all planes. When the non-
polarized light is made to pass through a polarizing filter, oscillations get oriented in only one
direction, and is called plane polarized light.

• Chiral molecules are optically active, which means that when a beam of plane-polarized light
passes through a chiral molecule, it interacts with the molecule in such a way that the angle of
the plane of oscillation rotates.

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 Polarimetry
• A pair of enantiomers always rotate plane-polarized light to an equal but opposite degree. If an
enantiomer rotates polarized light to the right or in a clockwise direction, it is said to be the (+) or
the dextrorotatory isomer. On the other hand, if the plane polarized light is rotated to the left or in
a counter-clockwise direction, the stereoisomer is called as the (−) or the levorotatory isomer.
• Enantiomers have the same physical properties, except for the direction in which they rotate plane

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polarized light. Since these isomers exhibit different optical activity, they are sometimes also
referred to as optical isomers.
• The angle of rotation allows you to ascertain the identity and quality of substances as well as their
concentration in mixtures. It can also indicate the progress of reactions and conversions.
Polarimeters are used in a wide range of applications, from the determination of the purity and
concentration of ingredients in pharmaceuticals to the maturity testing of agricultural products to the
measurement of the sugar content in beverages and candies.

Polarimeter.
Device used to measure the
angle rotation of an optically
active substance.
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 Application of Stereochemistry
• Stereochemistry may seem like a trivial subject because differences between stereoisomers are
usually subtle. In nature, however, and most importantly, in biological systems such as the human
body, these subtle differences have far-reaching implications.

• Natural amino acids are enantiomerically pure and are used as the building blocks of proteins and

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enzymes.

• Our ability to taste and smell is regulated by chiral molecules in our mouths and noses that act as
receptors to perceive foreign substances. Enantiomers may interact differently with the receptor
molecules and induce different sensations. For example, the two enantiomers of the amino acid,
leucine, have different tastes, one is bitter whereas the other is sweet. Enantiomers also can smell
different, as is known from the odors of the two carvones, where one has the odor of caraway and the
other of spearmint.

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 Epimers
• Epimers are diastereomers that contain more than one chiral center but differ from each other in
their absolute configuration at only one chiral center. Let's consider the following structures:

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• Both structures have the same molecular and structural formula but not the same conformation and
are not the mirror image of each other, therefore they are classified as diastereomers.

• These diastereomers differ from each other in the absolute configuration at only one chiral center.
Thus, we can conclude these molecules are epimers. In epimers the chiral carbon atoms whose
absolute configuration makes the two compounds different are called the epimeric carbons.

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 Meso Compounds
• A meso compound is an achiral molecule with multiple chiral centers that is superimposable on its mirror
image. These traits lead to specific qualities that meso compounds do not share with most other
stereoisomers.

• One such quality is the internal mirror plane. All meso compounds have something called an internal

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mirror plane. This internal mirror plane is simply a line of symmetry that bisects the molecule. Each half is a
mirror image of the other half.
• In this molecule, the upper and bottom sides are mirror images of each
other and are symmetric about the internal mirror plane (the dashed line
in the middle).
• Meso compounds must have a minimum of two chiral centers, with at
least one on each side of the internal mirror plane.

• Since meso compounds are achiral, they are considered optically inactive and cannot have an
enantiomer.

Not a meso compound, Not a meso compound, has 2 Not a meso compound, has 2 chiral It’s a meso compound, fulfills
because it only has one chiral centers but it cannot be centers can be evenly divided by halves, all previous requirements. 12
chiral center. evenly divided by halves. but halves are not mirrored images of
each other.
 Classroom Activity!
Which of the following structures are meso compounds? Explain why:

a) CH3C e)

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b) A
f)

c) a
Remember, a structure it’s considered to be a meso compound
when it fulfils all the of following criteria:
1. Have at least two chiral centers.
d) A 2. Have an internal mirror plane, that bisects the molecule
evenly.
3. The halves must be mirrored images of each other and must
have at least one chiral center at each side.
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 Assignments for next class
• Complete the exercises presented in assignment #9 and turn it in by or before
the deadline (0.66 points).

Prof. Fernando González Disla

• Presentation of research work group 5 (5 points).

• Investigate for the next class about Carbohydrates.

• Study and practice stereoisomers: chirality, diastereomerism, enantiomerism,

polarimetry, epimers, and meso compounds.

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 Do you have
any question?
Thank
You!
Prof. Fernando González Disla

[email protected]