Introduction to
Isomerism
Isomerism is a fundamental concept in organic chemistry
that describes molecules with the same molecular formula
but different arrangements of atoms. These isomers can
have dramatically different physical and chemical properties
despite having identical atomic compositions.
AP
by Chau Tran
Types of Isomerism
Constitutional isomers
Structural Isomerism are compounds
with the same molecular formula but
different structural formulas
Chain Isomerism
Definition Example
Chain isomers possess the Butane (C4H10) exists as n-
same molecular formula but butane (straight chain) and
different number of carbon isobutane (branched chain).
atoms in parent chains, which
can be straight or branched.
Position Isomerism
Definition Example
Compounds with the same molecular 1-Propanol and 2-Propanol are
formula but different positions of position isomers, differing in the
functional groups, multiple bonds, or location of the -OH group.
branches along the same parent
carbon chain length.
Fuctional Isomerism
Definition Example
Compounds with the same molecular Ethanol (CH3CH2OH) and dimethyl ether
formula but different functional (CH3OCH3) are functional group isomers.
groups.
Ring-Chain Isomerism
Definition Example
Isomerism arising from the Propene (CH3CH=CH2) and
difference between open-chain cyclopropane (C3H6) are ring-
and cyclic structures with the chain isomers.
same molecular formula.
Metamerism
Definition
Isomerism due to different
positions of polyvalent
functional groups (like S, N, O,
CO) in a molecule, with alkyl
groups around it.
Example
Tautomerism
Definition
A compound tend to exist in
two or more interconvertible
structures
Example
Fischer projection formulas are a way of representing three-
dimensional molecules in two dimensions.
Fischer Projection formula
Definition
• Fischer projection formulas are a way
of representing three-dimensional
molecules in two dimensions.
• The horizontal lines represent bonds
that pointing toward viewer, and
vertical lines represent bonds that
pointing far away from viewer.
• The central carbon atom is positioned
at the intersection of the horizontal
and vertical lines.
Fischer Projection formula
Rules
1. If Fischer projection is rotated by 180
degree at the plane of paper then it
=> identical molecule.
2. If Fischer projection is kept fixed at
one unit, rest all 3 units rotated
clockwise or anticlockwise direction
=> identical .
Fischer Projection formula
Naming Enantiomers based on R/S
• Often called Cahn-Ingold-Prelog rules
• A substituent with a higher atomic number takes precedence
over a substituent with a lower atomic number.
• When visualizing the molecule, the lowest priority
substituent should always point away from the viewer (a
dashed line indicates this).
• Draw an arrow from the highest priority atom to the 2nd
highest priority atom to the 3rd highest priority atom.
Because the 4th highest priority atom is placed in the back,
the arrow should appear like it is going across the face of a
clock. If it is going clockwise, then it is an R-enantiomer; If it
is going counterclockwise, it is an S-enantiomer.
• If there are two substituents with equal rank, proceed along
the two substituent chains until there is a point of difference.
Using Fischer projection to determine R/S
Optical activity
• Enantiomers have identical physical properties
• One feature set them apart is the interaction with
plane polarized light (PPL)
• PPL has light wave oscillating in a single plane
• Organic compounds can be classified as optically
active or optically inactive relating to ability to rotate
PPL
• Must have chirality for optical active
• The instrument that is used to measure
the extent to which plan rotate is called a
Polarimeter (using sodium light 589nm).
• If the rotation is clockwise, the compound is
called dextrorotatory, and the rotation is labeled d or
(+). On the other hand, if the plane of the light
rotates counterclockwise, we have
a levorotatory compound, and the rotation is labeled l
or (–).
D-L Configuration (Relative Configuration)
Definition Reference Significance
D-L system is used to describe Based on the configuration of Important in biochemistry for
the relative configuration of glyceraldehyde as a standard. describing the stereochemistry
molecules, especially in of naturally occurring
carbohydrates and amino acids. compounds.
Racemic Mixtures
Definition Properties Significance
A racemic mixture, or Racemic mixtures are optically Understanding racemic
racemate, is an equimolar inactive due to the cancellation mixtures is crucial in
mixture of a pair of of rotation by equal amounts of pharmaceutical development
enantiomers. each enantiomer. and chemical synthesis.
Diastereomers
Two cases:
1) Having multiple chiral centers, non-
superimposable, non-mirror image
2) Cis-Trans ((or E-Z system)
Configuration
Meso Compounds
1 Definition
Meso compounds are optically inactive compounds that contain
chiral centers but are superimposable on their mirror images.
2 Characteristics
Contains a plane of symmetry that divides the molecule into
two equal halves.
3 Example
Meso-tartaric acid is a classic example of a meso compound.
4 Significance
Understanding meso compounds is crucial for predicting optical
activity in molecules with multiple chiral centers.
Cis-Trans Isomerism (Geometrical isomers)
Definition Cis Isomer Trans Isomer
Cis-trans isomerism occurs In the cis isomer, similar groups In the trans isomer, similar
when there is at least one or atoms lie on the same side of atoms or groups lie on opposite
common group on both sides of the double bond or ring. sides of the double bond or
a double bond or site of ring.
restricted rotation.
Properties of Cis-Trans
Isomers
Property Cis Isomer Trans Isomer
Stability Less stable More stable
Dipole moment Higher Lower or zero
Polarity More polar Less polar
Boiling point Higher Lower
Melting point Lower Higher
E/Z System
Priority is based on CIP
rules similar to R/S
Newman Projections
• A Newman projection is a representation
of the molecule looking through a C-C
single bond.
• Each Newman projection represents the
bond between 2 carbons by a dot (front
carbon) and a circle (back carbon)
Conformers or Conformational Isomers
• Conformers are different arrangements of atoms that
occur as a result of rotation about single bonds.
• Most often, these rotations occur very fast at room
temperature => not considered as different
compounds
• Dihedral angle is the angle between
groups. Staggered
• When it = 00 => eclipsed conformation
• When it = 600 => Staggered
Eclipsed
ENERGY DIAGRAM
Tortional strain and Steric strain
• The torsional strain is
specifically for the eclipsing
groups. The increase in energy
resulting from eclipsing groups on
adjacent carbons is
called Torsional Strain
• Steric strain is caused by the
interaction between two bulky
groups
CHAIR CONFORMATION IN CYCLOALKANES
• Chair is the most stable, most
important, and common
conformation of cyclohexane
• When doing ring flip:
* Up stays Up, Down stays Down!
* Each Axial becomes Equatorial
* Each Equatorial becomes Axial
Exercises
1) Name Compounds
Exercises
2) Identify all the chiral centers in each Fischer projection and determine
the absolute configuration as R or S
3) Name the following alkenes
Conclusion: Importance of Isomerism in Chemistry
1 Structural Understanding 2 Property Prediction
Isomerism provides crucial insights into molecular Knowledge of isomers helps predict and explain
structure and bonding. differences in physical and chemical properties of
compounds.
3 Pharmaceutical Applications 4 Synthetic Chemistry
Critical in drug design and development, as different Understanding isomerism is essential for planning and
isomers can have vastly different biological activities. executing organic syntheses efficiently.
