Stereoisomerism

Occurs due to the restricted

rotation of C=C double bonds...
two forms CIS and TRANS
STRUCTURAL ISOMERISM
STEREOISOMERISM
GEOMETRICAL ISOMERISM
OPTICAL ISOMERISM
CHAIN ISOMERISM
Same molecular formula but
different structural formulae
Occurs when molecules have a
chiral centre. Get two non-
superimposable mirror images.
Same molecular
formula but atoms
occupy different
positions in space.
POSITION ISOMERISM
FUNCTIONAL GROUP
ISOMERISM
Geometric isomers
In alkenes
CIS
Groups/atoms are on the
SAME SIDE of the double bond
TRANS
Groups/atoms are on OPPOSITE
SIDES across the double bond
RESTRICTED ROTATION OF C=C BONDS

Single covalent bonds can easily rotate. What appears to be a different structure is
not. It looks like it but, due to the way structures are written out, they are the same.
ALL THESE STRUCTURES ARE THE SAME BECAUSE C-C BONDS HAVE FREE ROTATION
RESTRICTED ROTATION OF C=C BONDS

C=C bonds have restricted rotation so the groups on either end of the bond are
frozen in one position; it isnt easy to flip between the two.
This produces two possibilities. The two structures cannot interchange easily
so the atoms in the two molecules occupy different positions in space.
cis
trans cis
trans
Isomerism
Constitutional Isomers: Same atoms but
linked (bonded) together differently.
Spatial orientation not important.
3-methylpentane
hexane
cyclohexane
Are these constitutional isomers of hexane?
No, different molecular
formulae!!
Are these constitutional isomers of cis but-2-ene?
Not this one! It is 2-butene. Cis / trans
does not matter.
Stereoisomerism
Stereoisomers: Same molecular formulae,
same connectivity; same constitutional
isomer. Different spatial orientation of the
bonds.
Are these stereoisomers of cis but-2-ene?
How does the connectivity differ between these two?
Enantiomers and Diastereomers
Two kinds of Stereoisomers
Enantiomers: stereoisomers which are mirror
objects of each other. Enantiomers are
different objects, not superimposable.
Diastereomers: stereoisomers which are not
mirror objects of each other.
If a molecule has one or more tetrahedral carbons
having four different substituents then enantiomers will
occur. If there are two or more such carbons then
diastereomers may also occur.
Isomers, contain same atoms, same formula
Constitutional isomers, different
connectivities, bonding.
Stereoisomers, same connectivity,
different three dimensional orientation
of bonds
Enantiomers, mirror objects Diastereomers, not mirror objects
Summary of Isomerism Concepts
Mirror Objects Carbon with 4 different substituents. We
expect enantiomers (mirror objects).
Reflect!
These are mirror objects. Are they the same thing just viewed
differently ?? Can we superimpose them?
We can
superimpose two
atoms. but not all
four atoms.
The mirror plane still relates the two structures. Notice that we can
characterize or name the molecules by putting the blue in the back, drawing
a circle from purple, to red, to green. Clockwise on the right and
counterclockwise on the left. Arbitrarily call them R and S.
R
S
Arrange both
structures with the
light blue atoms
towards the rear.
Notice how the reflection
is done, straight through
the mirror!
Recap: Tetrahedral Carbon with four
Different Substituents. Enantiomers
Simple
Rotation,
Same
Simple
Rotation,
Same
Mirror objects.
Different, not
superimposable.

Enantiomers
But the reflection might have been done
differently. Position the mirror differently.
Reflection can give
any of the following
Can you locate the mirror
which would transform the
original molecule into each
mirror object?
In the course of each reflection,
two substitutents are swapped.
The other two remain
unchanged.
What is common to each of
these reflection operations?
All three of these structures are the same, just made by
different mirrors. The structures are superimposable.
What rotations of the whole molecules are needed to
superimpose the structures?

Again. all three objects on the
right are the mirror object of the
structure above. They are
different views of the
enantiomer.
A swap of two substituents is
seen to be equivalent to a
reflection at the carbon atom.
Now Superimposable mirror objects:
Tetrahedral Carbon with at least two identical
substituents.
Reflection can interchange the two red substituents.
Clearly interchanging the two reds leads to the same
structure, superimposable! Remember it does not
make any difference where the mirror is held for the
reflection.
This molecule does not have an enantiomer; the
mirror object is superimposable on the original, the
same object.
Polarized light vibrates in one plane only, in
contrast to ordinary light, which vibrates in
all planes.

What causes such a rotation of the plane of polarized liight?
According to the vant Hoff theory, such an effect on the plane polarized light
is due to the presence of one or more chiral carbon atoms.
Fischer projection
A two-dimensional method of indicating the structure of an enantiomer.
Horizontal lines indicate bonds extending forward from the paper and the
vertical lines indicate bonds extending backward from the paper.
The formulas are always written with the aldehyde(or ketone) group)-the
most highly oxidized-at the top.
CHO
C H OH
CH
2
OH
H OH
CHO
CH
2
OH
convert to
a Fischer
projection
Glyceraldehyde
(an aldotriose)
D (+) L (-)
C
C
CH
2
H OH
O
H
OH
C
C
CH
2
O H H
O
H
OH