Structure of Biological Macromolecules: Chirality

BMS1011
Structure of Biological
Macromolecules
Chirality
Prof. Tanja Junkers

School of Chemistry
Email: [email protected]
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Learning outcomes
At the end of this session, you should be able to:
• Understand constitutional isomers

• Identify cis-trans and E/Z isomerisation
• Identify stereocentres in molecules and calculate the number of

stereoisomers
• Assign R and S chiral configuration
• Understand the requirement for stereoisomer; enantiomers and
diastereoisomers
• Understand the importance of chirality in the biological world
Isomers
Isomers are molecules that have the same molecular formula, but have
a different arrangement of the atoms in space.
• Constitutional isomers
• In structural (constitutional) isomerism, the atoms are
arranged in a different order.
• Stereoisomers
• In stereoisomerism, the atoms are arranged in the same
order, but in different 3-dimensional orientation
Constitutional Isomers
They have different physical and chemical properties
CH 3 CH 2 OH
Ethanol bp
78°C
CH 3 OCH 3
Dimethyl ether
bp-24°C
Constitutional Isomers
Draw all the constitutional isomers of C6H14
Cis-trans isomers
Cis-Trans Isomers
Depending on whether the
substituents of highest priority at
each end of the double bond are
next to or opposite each other
E & Z Isomers
The E, Z system must be used for
tri- and tetra-substituted alkenes
To assign an E, Z configuration, first
assign a priority to the substituents
on each side of the double bond
Entgegen Zusammen
Priority based on atomic number (opposite) (together)
Chirality
https://www.youtube.com/watch?v=JS-iAuCIexk
Chirality
…is all around us
Chirality
…in chemsitry
chiral
Chirality
…in chemsitry
achiral
Chirality
• A molecule (or object) that is not superposable on its

mirror image is described as being chiral.
• It is all about symmetry!
• Many chiral molecules contain an asymmetric carbon

centre, a so called stereogenic centre.
• This is easily identified as a carbon atom attached to
four different groups.
Stereoisomers - Enantiomers
Example: Lactic acid = 2-Hydroxypropanoic acid
• Lactic acid and its mirror image are non-superimposable.
• Stereoisomers that are mirror images of each other are enantiomers.
• Enantiomers do not differ in their physical characteristics, yet interact

differently with polarized light and with stereospecific environments!
Asparagine
mirror
plane
O OH HO O
C C
H2N C H H C NH2
CH2 CH2
C C
H2N O O NH2
L-asparagine (from D-asparagine (from
asparagus) bitter vetch) sweet taste
taste
(+) and (-) refers to optical activity of the compounds

Achiral compounds
If an object and its mirror image are superimposable, they are
identical, they are called achiral (without chirality).
An object or molecule is achiral if it has a plane of symmetry. A

plane of symmetry is an imaginary plane passing through an object
dividing it such that one half is the mirror image of the other half.
Naming
HO H H OH
H3C COOH HOOC CH3
How do we name these lactic acid enantiomers unambiguously?
• Use the Cahn, Ingold, Prelog system of nomenclature

• Used to designate configuration at a stereocentre
• The labels R and S are used to differentiate between
enantiomers
More in Tutorial
Naming
1. Locate the stereogenic centre and identify each of the four

substituents.
2. Assign a priority (1 to 4) to each substituent*.

1 4
3
2
3. Orient the lowest priority substituent away from you. (i.e.

group/atom = 4, this is usually a hydrogen atom). The
remaining three groups then project towards you.
4. Look at the molecule so that group 4 point away from you
5. Read the groups from 1→ 3.

If the reading is clockwise, the stereochemistry is
designated as R (Latin: Rectus, right)
If the reading is anticlockwise, the stereochemistry is
designated as S (Latin: Sinister, left)
• For a molecule with 1 stereocentre, 21 = 2 stereoisomers
are possible
• For a molecule with 2 stereocentres, a maximum of 22 = 4

stereoisomers are possible
• For a molecule with n stereocenters, a maximum of 2n

stereoisomers are possible
8 stereocenters
256 stereoisomers
are possible
Stereoisomers - Diastereoisomers
Consider a compound
with two stereocentres
It has two stereocentres; 22

= 4 stereoisomers exist
Diastereoisomers
Diastereoisomers:
Stereoisomers that are not
mirror images and cannot
be superimposed
Stereoisomers – Meso compounds
Tartaric acid has two chiral centers
2R,3R and 2S,3S are chiral
However, 2S,3R and 2R,3S are no enantiomers!
Mesoform
Enantiomers and biology
• Enzymes: chiral substances which only produce or react
with substances that match their stereochemical
requirements
• Enzymes can distinguish between different enantiomers
of glyceraldehyde
Summary and learning outcomes
After this lecture you should be able to:
• Understand constitutional isomers

• Identify cis-trans and E/Z isomerisation
• Identify stereocentres in molecules and calculate the number of

stereoisomers
• Assign R and S chiral configuration
• Understand the requirement for stereoisomer; enantiomers and
diastereoisomers
• Understand the importance of chirality in the biological world
Overview
Useful links
Enantiomers and Diastereoisomers

https://www.youtube.com/watch?v=paEjN_KWf_w
Meso compounds
https://www.youtube.com/watch?v=bzYsE_hnC9g
R and S nomenclature
https://www.youtube.com/watch?v=Z10oC7BF4ig

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BMS1011

Prof. Tanja Junkers

The material in this communication may be subject to copyright

Any further reproduction or communication of this material by you

Do not remove this notice.

• Understand constitutional isomers

• Identify stereocentres in molecules and calculate the number of

They have different physical and chemical properties

• A molecule (or object) that is not superposable on its

• Many chiral molecules contain an asymmetric carbon

• Lactic acid and its mirror image are non-superimposable.

• Stereoisomers that are mirror images of each other are enantiomers.

• Enantiomers do not differ in their physical characteristics, yet interact

(+) and (-) refers to optical activity of the compounds

An object or molecule is achiral if it has a plane of symmetry. A

H3C COOH HOOC CH3

How do we name these lactic acid enantiomers unambiguously?

• Use the Cahn, Ingold, Prelog system of nomenclature

1. Locate the stereogenic centre and identify each of the four

2. Assign a priority (1 to 4) to each substituent*.

3. Orient the lowest priority substituent away from you. (i.e.

5. Read the groups from 1→ 3.

• For a molecule with 2 stereocentres, a maximum of 22 = 4

• For a molecule with n stereocenters, a maximum of 2n

It has two stereocentres; 22

2R,3R and 2S,3S are chiral

However, 2S,3R and 2R,3S are no enantiomers!

• Understand constitutional isomers

• Identify stereocentres in molecules and calculate the number of

Enantiomers and Diastereoisomers

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