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BIOL 157: BIOLOGICAL CHEMISTRY

• J. K. Dadson, PhD

• Department of Biochemistry and Biotechnology,

• Office: SCB, RM B5
jaydadson1990@[Link]
•
Lecture 3:
Isomerism
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Study Objectives
• In this lecture, we aim to learn more about the following;

Structural or constitutional isomerism

Geometric isomerism

Optical isomerism
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Introduction
It is a common feature to come across compounds with the same molecular
formula but with different physical and chemical properties

These differences in properties may be slight or very remarkable

The reason for the difference may be due to how the constituent atoms are
linked to each other or how they are arranged in the 3-D space

Isomerism therefore is a situation where compounds having the same molecular

formula can be represented by different structures
 Types of Isomerism
There are two primary types of isomerism, which can be
further categorized into different subtypes.

These primary types are

Structural Isomerism

Stereoisomerism.
 Structural Isomerism
Structural isomerism is commonly referred to as constitutional isomerism.

They differ in the way the constituent atoms are linked or connected to each
other.

Different structural isomers are assigned different IUPAC names since they
may or may not contain the same functional group.

The different forms of constitutional/structural isomers are

Chain isomers
Positional isomers
Functional group isomers
Tautomers etc.
 (a) Chain Isomerism
It is also known as skeletal isomerism.

The components of these isomers display differences in the way

atoms are arranged as straight chains or as branched compounds.

Commonly, chain isomers differ in the branching of carbon.

An example of chain isomerism can be observed in the compound

C5H12
• Try to draw the two isomeric forms of butane C4H10
 (b) Positional Isomerism
The positions of the functional groups or substituent atoms are different in position
isomers.

Typically, this isomerism involves the attachment of the functional groups to

different carbon atoms in the carbon chain.

An example of this type of isomerism can be observed in the compounds having
the formula C3H7Cl and C3H8O
 (c) Functional Isomerism
It is also known as functional group isomerism.

As the name suggests, it refers to the compounds that have the same chemical
formula but different functional groups attached to them.

An example of functional isomerism can be observed in the compound C3H6O

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Try
• C2H6O

Ethanol Dimethyl ether/

Methoxymethane
 (d) Tautomerism
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.

They are interconvertible structures that differ at the relative

position of one atomic nucleus usually the hydrogen (proton)

It occurs via an intramolecular proton transfer.

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 Stereoisomerism
Compounds having the same chemical formula but different
orientations of the atoms in three-dimensional space.

 The compounds that exhibit stereoisomerism are often referred to

as stereoisomers.

This phenomenon can be further categorized into two subtypes.

Geometric Isomerism
Optical Isomerism
 Geometric Isomerism
This type of isomerism is due to hindered rotation about a double bond system or a
ring system. The presence of c=c introduces remarkable rigidity in the molecule

It is popularly known as cis-trans isomerism. These isomers have different spatial
arrangements of atoms in three-dimensional space.

An illustration describing the geometric isomerism observed in the acyclic But-2-
ene molecule is provided below.
Note that as a result of the double bond, it is not possible to obtain the cis from
the trans just by rotating one of the doubly bonded carbons as it may appear so.

Therefore, the two isomers are two different compounds with different physical
properties

Cis-trans isomers differ in stability, boiling point and melting point

Take cis- butanedioic acid (maleic acid) and trans butanedioic acid (fumaric acid)
for instance

Fumaric acid Maleic acid

With the COOH groups being so close in the cis-isomer, there can be
interaction between them, leading to the elimination of water to form a ring
anhydride at about 150oC

The anhydride can readily be reconverted to the cis-isomer in the presence of

water. The trans isomer cannot form such anhydride

In living cells, there can be hydration of fumaric acid in a reaction catalyzed by
an enzyme called fumarase.

The enzyme fumarase is stereospecific for fumaric acid but not the cis (Maleic
acid)
A similar situation can be seen in ring structures where the ring introduces
molecular rigidity and causes geometric isomerism
 Optical Isomerism
Arrangement of atoms in molecules (of the same molecular formula) may cause
interaction with plane polarized light.

Molecules that are able to interact with plane polarized light are said to be
optically active and so show optical isomerism.

Depending on the spatial arrangement of the component atoms, optically active

compounds may rotate the light either to the right or to the left.

Compounds that rotate the light to the right are said to be dextro-rotatory and
those that rotate to the left are levo-rotatory.
 Why Some compounds are Optically
Optically Active
active compounds are tetrahedral in structure with four different
groups bonded to the central carbon.

Such a carbon becomes an asymmetric carbon with a chiral center or a

stereogenic center.

Therefore, optically active compounds are also chiral molecules.

Optical isomers that are related as an object is related to its mirror image are
termed enantiomers. Those that are not mirror images are Diastereoisomers
Some optically active compounds may have more than one isomers due to
presence of several chiral carbons.

The number of optically active isomers a compound can have may be

calculated as 2n where n refers to the number of chiral centers
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 Let's take the case of tartaric acid as an example.

 Properties of Enantiomers
1) The physical properties of enantiomers, like melting point, boiling point, density
and solubility in common solvents are identical. However, the direction of plane
polarized light differs.

2) Enantiomers form crystals of the same type except that one crystal is the mirror
image of the other. The two are called enantiomorphs.

3) The chemical properties for enantiomers are identical for the reactions with
compounds which are not optically active. Reaction rates may differ with optically
active compounds.

4) Enantiomers have different physiological properties. For example, (-) -adrenaline is

more active in contracting blood capillaries than (+) -adrenaline. Then, (-) -nicotine
 Racemic Mixtures
These are equimolar mixtures of two optically active isomers.

Such mixtures are optically inactive due to external compensation. Eg. (+)-lactic
acid and (-)-Lactic acid when mixed in equal proportions gives a racemic mixture
which is optically inactive.

Racemic mixtures can be separated in a number of ways. The separation of

racemic mixtures is called Resolution.
Some biological systems are able to separate racemic mixtures. Penicillium glaucum are
able to utilize (+)-lactic acid but not the (-)-Lactic acid.
Affinity chromatography can be another means of separation
Combining racemic mixture with a chiral molecule (chiral resolving molecule).
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Lecture 4:
Functional Groups
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Objectives
To consider the various functional groups present in organic
compounds.

To identify reactions between alcoholic and carbonyl functional

groups leading to formation of hemiacetals, hemiketals, acetals
and ketals in carbohydrates.
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Functional Groups
There are myriads of organic compounds which can either be natural or
synthetic

Compounds undergo specific reactions due to their chemical properties.

The chemical properties are dependent on both the chemical structure and
the functional group of the organic compound.

Consider Ethane, Ethanol and propanoic acid

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Alcohols have the hydroxy functional group, organic acids have carboxylic acid
functional group and aldehyde and ketones have a carbonyl functional groups.

Functional groups are therefore atoms or groups of atoms which when present,
determine both the physical and chemical properties of a compound.
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Hemiacetals, Acetals, Hemiketals and Ketals

Alcohol and carbonyl compounds react to form several biologically important

compounds.

Hemiacetals and hemiketals are formed through reversible reactions involving

alcohols and carbonyl compounds.

This is a nucleophilic addition reaction.

The nucleophilic addition is attributed to the chemical nature of the functional

groups (ie. Hydroxyl and carbonyl functional groups).
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A hemiacetal is formed from an equilibrium mixture one mole of aldehyde and

alcohol through a nucleophilic addition.

This reaction is catalysed by a trace of strong acids.

In a hemiacetal, a carbon atom holds both OH and OR group.

Hemiacetals are not stable.

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A hemiketal is formed from an equilibrium mixture one mole of

ketone and alcohol through a nucleophilic addition.

Given an equimolar amount of alcohols and carbonyl compounds,

The relative concentration of the hemiketal is less than hemiacetal.
This is due to the difference in reactivity between aldehyde and ketones.
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The addition of an alcohol molecule to a hemiacetal results in the

formation of an acetal.

It involves a condensation reaction where there is elimination of

water.

Acetals are stable compounds and can be isolated and purified.

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A ketal is a functional group derived from a ketone by

replacement of the carbonyl (C=O) group by two alkoxy groups
(OR).

Ketals are formed from the addition of an alcohol molecule to a

hemiketal.
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Hydrolysis of Acetals and Ketals

This involves the breakdown of acetals and ketals to give an
aldehyde or ketone and two molecules of alcohol.

The hydrolysis takes place in the presence of an acid catalyst or

an enzyme.
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