Lecture 3 - Recap

 Different types of isomers

 Stereochemistry
 Symmetry and asymmetry
 Chirality
 Asymmetric centre/ Chiral Carbon
 Stereogenic Centre
 Enantiomers
 Plane of symmetry & center of symmetry
Stereochemistry-II
 Configuration
Configuration of a molecule is the detailed
stereochemical picture including how the atoms
are arranged in space.
It is represented (specified) by letter ‘R’ or ‘S’.
For doing this, we assign priority numbers
according to Cahn-Ingold-Prelog system and see
which way the priority numbers are arranged.
 If priority numbers are arranged clockwise,
then specification is ‘R’.
If priority numbers are arranged anticlockwise,
then specification is ‘S’.
 Wedge – Dash & Fischer Projections

How do we represent a three dimensional molecule

on to a two dimensional plane i.e. blackboard or
paper?
By, Wedge-and-dash drawing (perspective diagram)
or
By Fischer’s projection formula (also called cross
formula).
We will concentrate in our discussions on molecular
representation by Fischer’s formula mainly as it is
difficult to represent molecules with many chiral
carbon atoms by Wedge and dash form.
 Wedge – Dash Representation
Usually drawn with two bonds in the plane of the page,
one in front, and one behind to give the molecule
perspective. When drawing wedge-dash it is a good
practice to visualize the tetrahedral arrangement of the
groups and try to make the diagram "fit“ this.
 Fischer Projections
How is Fischer’s formula drawn?
We draw two lines (one vertical and one/( two or
more) horizontal line(s)) depending upon the
number of stereocenter/(s) in the molecule.
The point of intersection of these lines is considered
as representing the stereocenter.
The formula can be drawn only for molecules with
stereocenter.

Fischer’s formula for Lactic acid is

 Fischer Projections
The horizontal lines represent wedges (bonds)
coming out of the plane of paper.

The vertical lines represent dashed lines (bonds)

going into the plane of the paper.

When drawing Fischer Projection the carbon chain is

drawn along the vertical line of the projection, with
the most highly oxidized carbon substituent at the
top.
Conversion of Wedge – Dash to Fischer Projections
 Configuration
While assigning configurations using fisher
Projections:
If the lowest priority number is along vertical
line (may be above or below) then assigned
specification remains same.
If the lowest priority number is along
horizontal line (on the left or right of the
stereocenter) then assigned specification will
be opposite to the specification we got.
 Cahn-Ingold-Prelog Rules
Assign a priority number to each group
attached to the chiral carbon.
Atom with highest atomic number -
assigned the highest priority #1.
In case of ties, look at the next atoms along
the chain.
Double and triple bonds are treated like
bonds to duplicate atoms.
 Cahn-Ingold-Prelog Rules
Rule 1: Priority number is
assigned on the basis of
atomic number of atom
bonded to stereocenter.
I > S > O > N > 13C > 12C > Li > 3H (T) > 2H (D) > H

Example 1 In this example the priority numbers

are arranged anticlockwise and the lowest
priority number is along vertical.
Therefore specification is ‘S’ (Latin, sinister =
left).
 Cahn-Ingold-Prelog Rules
H
Rule 2: Priority number is
assigned on the basis of 1 2
Cl CH3
mass number if isotopes
are bonded to stereocenter.
3
D
Example 2 In this example the priority numbers
are arranged clockwise and the lowest priority
number is along vertical.
Therefore specification is ‘R’ (Latin, rectus =
upright).
 (R) and (S) Assignments

(a)The molecule is drawn is 3

(1) (1)
dimensions, and arranged NH2
(2) (2)
NH2

*C CO2H HO2C
C*
in such a way that the bond H CH3 H3C H
(4) (4)
(3)
between the chiral carbon unnatural
(3)
natural
alanine alanine
and the lowest priority
groupheads back into the
paper.
(1) (1)
NH2 NH2
C* C*
(b) Draw an arrow from the H3C
(3)
CO2H
(2)
HO2C
(2)
CH3
(3)
group of highest priority,
to the second, to the third (R) enantiomer (S) enantiomer

priority group.
 Assign (R) or (S)
Working in 3D, rotate molecule so that lowest
priority group is in back.
Draw an arrow from highest to lowest
priority group.
Clockwise = (R), Anticlockwise = (S)
Assign (R) or (S)
2

3
CH3

2
R
C2H5 1

C3H7
 Cahn-Ingold-Prelog Rules
1
Cl
CH3
Rule 3: In the case of the same
atoms being bound directly to H 2
C CH3
the chiral carbon, we go to the
3 CH3
next atoms along the chain till CH
Priority number is determined. CH3 CH3

-CH2Br > -CHCl2 > -C(CH3)3 > -CH(CH3)CH2F >

-CH(CH3)2 > -CH2CH3
Example 3 In this example the specification is
‘S’.
 Example
H 1 H
H CH3
Cl
Cl C C OH
H C C C H
H C ? ? C OH
H
H H H
4 H

C(C,C,H) and C(C,C,H) do not show any difference

 Example contd..
C(C,C,H) and C(C,C,H) do not show any difference

Two sub- H H Two sub-

H CH3 branches
branches Cl
Cl C C OH on right are
on left
are H C C C H arranged:
arranged: H C H C OH C(O,C,H) >
C(Cl,H,H) H H H
> H C (O,H,H)
C(H,H,H)
Considering senior sub-branches it yields C(Cl,H,H)
> C(O,C,H). (No need to consider junior sub-
branches).
 Example contd..
1
H H
H CH3 1
Cl
Cl C 2 3 C OH
H C C C H S
H C
H C OH
H H H 2 3
4 H

Priority of left hand side group is higher than right

hand side
 Cahn-Ingold-Prelog Rules
Rule 4: Double and
triple bonds are
treated as if each bond
were to a separate
atom. (Imagine that
each  bond is broken
and that the atoms at
both ends were
duplicated. When a
bond is broken only
two imaginary atoms
are added).
 Cl
H

H2C C CH2CH3
H OH
S
O

HO H

H3CH2C H S
CH3
O OH
H
H3C CH2CH3

3S and 4S
 CH3
CH2NHCH3
Cl
NH
HO
OH
H

HO
O

S R