CHM209: INTERMEDIATE ORGANIC

CHEMISTRY

TITLE:
STEREOCHEMISTRY

GROUP : AS115 2B

LECTURER’S NAME : MS. NURHAFIZAH BINTI MOHD SELIHIN

DATE OF SUBMISSION : 17TH MARCH 2017

 1.0. INTRODUCTION

Stereochemistry’s foundations were led by Jacobus van’t Hoff and Joseph Achille Le
Bel in 1874. Jacobus van’t Hoff and Joseph Achille Le Bel independently proposed that the
four bonds to the carbon were directed towards the corners of tetrahedron.

Stereochemistry is the study of the branch of the chemistry which concerned with the
three-dimensional (3-D) structures of molecules of organic or inorganic chemistry and the
effects of such arrangements on physical and chemical properties of the molecules.

Example:

Perspective formula of
methane 3-D structure of methane
(3-D structural formula of methane) (Ball and stick model of 3-D
                                                                                                               structure of
methane)

Isomers can be classified either as constitutional isomers or also known as structural

isomers and stereoisomers. In the other hand, stereoisomer category has several further
subcategories; geometrical isomers: cis-/ trans- isomers and stereocentres.

Constitutional isomers or structural isomers are the compound that has same
molecular formula but different structure and
different names.

Example:
 Isomers that have the same constitution but differ in the spatial arrangement of their
atoms are called stereoisomers. The first subcategory of stereoisomers is geometric
isomers (also called cis-/trans- isomers) are a type of stereoisomer resulting from a double
bond or a ring structure.

Example:

Structural formula of cis-2-butene and trans-2-butene

Another subcategory of stereoisomers is called stereocentres. Stereocentre is a

stereoisomer that contains an asymmetric centre. In the study of chemistry, asymmetric centre
is an atom bonded to different types of groups in a way that the mirror image is not
superimposable on the original image.

Example: A right hand and a left hand are mirror images of one another that cannot
be superimposed.
 2.0 DISCUSSION

1. CHIRAL AND ACHIRAL

In 1894, William Thomson (Lord Kelvin) defined an object as chiral if it is not

superimposable on its mirror image.
Applying Thomson’s term to
chemistry, it is found that a molecule
is chiral if its two mirror image
forms are not
superimposable in 3- dimension.

Chiral compound is
any molecule that is non-superimposable with its mirror image. It has enantiomers of
opposite configuration. The asymmetric centres usually have different types of groups
attached to it, therefore when a plane of symmetry cuts a chiral compound; the other half of
the molecules is not a reflection of the other half.

Example: Bromochlorofluoromethane

No matter how the molecule is rotated, it cannot be superimposed on its

    mirror image.
 On the other hand,
achiral compound
is the opposite of chiral compound. Achiral compound is any molecule that is superimposable
with its mirror image. The enantiomers of achiral compound are identical. The asymmetric
centres usually have two similar groups attached to it, therefore, when a plane of symmetry
cuts an achiral compound, the other half of the molecules is a reflection of the other half.

Example: Bromochloromethane

If (b) is rotated 180°, structure (c) is obtained which can be superimposed

                          on structure (a). Therefore, they are identical to their mirror image.
 Perspective formula of bromochloromethane and its mirror image

2. ASYMMETRIC CARBON

Asymmetric carbon is a carbon atom that is bonded to four different atoms or groups.
In 1996, the IUPAC recommended that tetrahedral carbon atom that bears four different
atoms or group to be called as chirality centre.

Asymmetric carbon is usually indicated by an asterisk (*).

Example: The asymmetric carbon is bonded with four different groups.

 Isomers with one asymmetric
carbon exist as two different
stereoisomer. The structure of the
isomers can be expressed by using
Perspective Formula; where the two solid
lines and a wedged line marks any four
groups that can be bonded to the asymmetric carbon while the dashed line indicates the
lowest priority group that bonded to the asymmetric carbon.

Perspective formula Perspective formula of 2-bromobutane

In the other hand, isomers with more than one asymmetric carbon can be expressed by using
staggered or eclipsed perspective formula:
The more the asymmetric carbon a compound has, the more stereoisomers are possible for
the compound. A compound can have a maximum number of stereoisomers; 2 n, where n is
the number of asymmetric carbon.

3. ENANTIOMER

Enantiomer is mirror image that is non-superimposable to its original structure.

Enantiomer, which came from the Greek word enantios, which means ‘opposite’. Enantiomer
have opposite configuration at all stereocentre of a molecule. This can be explained as the
mirror image of a molecule cannot be placed on top of the original structure.

Enantiomers have identical chemical and physical properties with their mirror image
and the original structure except for their ability to rotate on plane-polarized light (+/-) by
equal amount but in opposite directions.
 Example:

These molecules are mirror image towards each other. Since the asymmetric carbon is
bonded with four different groups, it is a chiral compound. The mirror image of [a] is
non-superimposable to [b]. Therefore, these molecules are enantiomer towards each
other.

The perspective formula of 2-bromobutane and its mirror image

Since enantiomer are two different compounds with two different configurations; to
distinguish between these compounds, the usage of prefix R or S to the IUPAC name of the
enantiomer is used. R means ‘rectus’ which means right and S is for ‘sinister’, which means
left.

Example:
 [a] = S-2-bromobutane [b] = R-2-bromobutane

4. DIASTEREOMER

Stereoisomers that are not related to as an object and its mirror image are called
diastereomers. The stereoisomers are similar in the term of molecular formula, but they are
not identical the term of physical structure and they are also not mirror image to the original
compound.

Example:
From the diagram above, it is noticed that structure C and D is not mirror image of structure
A and B and does not share the same physical structure of structure A and B. Therefore;

Structure A is diastereomer for structure C and structure D

Structure B is diastereomer for structure C and structure D

5. MESO COMPOUND

A chiral compound that contains tetrahedral stereogenic centres due to the presence of
plane of symmetry are called meso compound. Mesos is the Greek word for “middle”. A
meso compound does not rotate plane-polarized light because it is superimposable on its
mirror image.

A meso compound has two or more asymmetric carbons and a plane of symmetry. A
plane of symmetry is a mirror plane that cuts the molecule in half, so that one half of the
molecule is a reflection of the other half. A molecule with a plane of symmetry does not have
an enantiomer. If a compound has a plane of symmetry, it will not be optically active and will
not have an enantiomer, even though it has asymmetric centers.
 A compound with the same four atoms or groups bonded to two different asymmetric
carbons will have three stereoisomers; one of the stereoisomers will be a meso compound and
the other two of the stereoisomers will be enantiomers.

Example:

Structure A and B are non-superimposable mirror image. Therefore, both structures

are enantiomers.

From
structure A, the
position of
bromine and
hydrogen is
shifted as hydrogen should be bonded with asymmetric carbon on the dashed line.

Therefore, structure C is a new stereoisomer.

 Structure C and D are superimposable mirror image. Therefore structure D is not
stereoisomer.

Since structure C and D are identical, therefore structure C is a meso compound and has two
identical halves when a mirror plane cuts structure C in half.

4.0. CONCLUSION

Chemistry in 3-dimensions is known as stereochemistry. At its most fundamental level,

stereochemistry deals with molecular structure. A molecule is chiral if it cannot be
superimposed on its mirror image while molecules in which mirror image are superimposable
are achiral compound. Non-superimposable mirror images are enantiomer of one another.
Both enantiomers of the same substance are identical in most of their physical properties.
Stereoisomers that are not mirror image are classified as diastereomers.

The most common kind of chiral molecule contains a carbon atom that bears four different
atoms or groups; such an atom is called an asymmetric carbon. For a particular constitution,
the maximum number of stereoisomers is 2n, where n is the number of asymmetric carbon
Achiral compounds that contains chirality centres are called meso compound.
5.0 REFERENCES

1. Books

i) Francis A. Carey. (2006). Organic Chemistry, Sixth Edition. McGraw-Hill, New York
10020.

ii) Janice Gorzynski Smith. (2017). Organic Chemistry, Fifth Edition. McGraw-Hill
Education, United States of America

iii) McMurry, Simanek. (2007). Fundamentals of Organic Chemistry, Sixth Edition.

Thomson Brooks/Cole, United States of America

2. Internet

i) Prof. Mark Lipton. (2014). Stereochemistry Retrieved from

https://chem.libretext.org/LibreTexts/Purdue/Purdue
%3A_Chem_26505%3A_Organic_Chemistry_I_(Lipton)/Chapter_3._Stereochemistry