BCH 201
Stereochemistry
Stereoisomerism
This is a phenomenon by which compounds have
the same atomic connectivity but differ in the
spatial arrangement of the constituent atoms.
Isomerism
There are three major types of isomerism:
• constitutional isomerism
• geometrical isomerism
stereoisomerism
• optical isomerism
Constitutional isomers
Constitutional isomers (also known as structural isomers)
have the same molecular formula but differ in the sequence
in which the individual atoms are bonded (connectivity).
• skeletal isomerism
C
C C C C and C C C
• positional isomerism
OH OH
NO2
and
NO2
Constitutional isomers
Functional isomers: - compounds of identical
molecular formula but which have different functional
groups.
e.g. C2H5OH and CH3OCH3
Stereoisomerism
Stereoisomers have the same atomic connectivity
but differ in the spatial arrangement of the
constituent atoms.
H 3C CH 3 H 3C H
C C C C
H H H CH 3
CO2H CO2H
H 3C H H CH3
NH2 H 2N
alanine
Enantiomers
Enantiomers are stereoisomers that are non-superimposable
on their mirror images.
mirror
C C
A B B A
D D
CO2H CO2H
H 3C H H CH3
NH2 H2N
Diastereomers
Diastereomers are stereoisomers that are not mirror images
of each other – they are stereoisomers that are not
enantiomers.
H 3C CH 3 H 3C H
C C C C
H H H CH 3
Chirality
Molecules that can exist as enantiomers are said to be
chiral; they are non-superimposable on their mirror
images.
Chirality is a necessary and sufficient
condition for the existence of enantiomers.
“cheir” - Greek meaning “hand”
Molecules that are superimposable on their
mirror images are said to be achiral.
Tetrahedral stereogenic centres
A carbon atom bonded to four different groups is
called a tetrahedral stereogenic centre, asymmetric
centre, or chirality centre.
H*
(+)-carvone
(+)-Carvone is responsible for the odour of caraway seed oil.
Stereogenic centres
A centre where a swapping of groups leads to a
stereoisomer:
H 3C CH 3 H 3C H
C C C C
H H H CH 3
CO2H CO2H
H 3C H H CH3
NH2 H 2N
alanine
van’t Hoff and Le Bel
mirror
A A
B D D B
C C
The two are non-superimposable, mirror images. Such isomers
are called enantiomers
Are these enantiomers?
A A
B A A B
C C
Configurations
The particular arrangement of atoms in space that is
characteristic of a given molecule is called its
configuration.
Configurations are not the same as conformations.
Conformations are interconvertible by rotation about
single bond(s) whereas bonds must be broken to
change one configuration into another.
How do we “draw” a chirality centre?
C 2H 5 C 2H 5
H Cl Cl H
CH3 CH3
C2H5 C2H5
H CH3Cl Cl CH3H
How do we “draw” a chirality centre?
C2H5 C2H5
H CH3Cl Cl CH3H
C 2H 5 C 2H 5
H Cl Cl H
CH 3 CH 3
Fischer structures......
Properties of enantiomers
Physical: Enantiomers have identical physical properties
with the exception that they rotate the plane of polarized
light in opposite directions although || is identical.
Chemical: They have identical chemical properties
except for their reaction with reagents which are,
themselves, optically active. In this case, reaction rates
differ and depend on which enantiomer of the reagent is
used.
(+)-Glucose is central to the fermentation process
whereas (-)-glucose doesn’t react!
Plane-polarized light
Ordinary light is a moving wave whose vibrations take
place in all directions perpendicular to the direction in
which the light is travelling. One can envisage each
vibration as the vector of two vibrations which are
mutually at right angles.
One of these components can be eliminated by passing
ordinary light through a polarizer - Polaroid filter. The resulting
light is said to be polarized - all its vibrations are parallel to a
single plane.
Polarimeter
sample
tube
source polarizer analyzer
5893 Å
Optical activity
An optically active compound is one which rotates the
plane of polarization.
If from the vantage point of the observer the rotation is in
the clockwise direction, the sample is said to be
dextrorotatory. The angle of rotation, , is considered to be
positive (+).
If the rotation is in the counterclockwise direction, the
sample is said to be levorotatory and the angle, , is then
negative (-).
Racemic mixtures
An equimolar mixture of two enantiomers.
Prefix the name with +
When reactions are performed using an achiral reagent to
form products with a tetrahedral stereogenic centre, such
product will be a racemic mixture.
However, if the reagent is chiral, one can often produce a
single enantiomer of the product molecule.
How many stereoisomers exist?
The maximum number of stereoisomers that can
exist is equal to
2n
where n is the number of tetrahedral stereogenic
carbons in the molecule.
2,3-dichlorobutane
Look at 2,3-dichlorobutane. Are there four different isomeric forms?
Answer: YES
* *
CH3-CH-CH-CH 3
Cl Cl
There are two tetrahedral stereogenic carbons.......2n?
2,3-dichlorobutane
CH3 CH3
(2S,3S) H Cl Cl H (2R,3R)
Cl H H Cl
CH3 CH3
CH3 CH3
(2S,3R) H Cl Cl H (2R,3S)
H Cl Cl H
CH3 CH3
THANK YOU
FOR
YOUR ATTENTION
