Stereochemistry

➢ Stereochemistry refers to the 3-dimensional properties and reactions of molecules.

➢ For example, most drugs are often composed of a single stereoisomer of a compound.
Among stereoisomers one may have positive effects on the body and another
stereoisomer may not or could even be toxic.

➢ It has its own language and terms that need to be learned in order to fully communicate
and understand the concepts
 Isomers
(Different compounds with same molecular formula)

Constitutional isomers Stereoisomers

(differ in connectivity) (differ in 3-D arrangement)

Coformational isomers Configurational isomers

Cis-trans isomers Optical isomers

 Chirality
(Handedness)

Chiral: molecules which are not superimposable

upon its mirror image

Achiral: molecules which are superimposable on

their mirror images
Chiral centre: Chiral centre/
Stereo genic centre
• Also called asymmetric centre
• Carbon atom that is bonded to four different groups
is chiral
• Its mirror image will be a different compound
(enantiomer)
 IUPAC – Absolute Configuration

Chiral centre

*
 R and S configuration
Cahn-Ingold Prelog system:
• The order of rearrangement of four groups around a chiral carbon is called the
absolute configuration around that atom

• System which indicates absolute configuration was given by three chemists R.S.
Cahn, C.K. Ingold and V. Prelog

• The letter (R) comes from the Latin rectus (means right) while (S) comes from the
Latin sinister (means left).

• Any Chiral carbon atoms have either an (R) configuration or a (S) configuration.

• Therefore one enantiomer is (R) and the other is (S).

Rule 1: Priority order

• The atom having highest atomic number gets the highest priority

• If two or more than two isotopes of the same element are

present, the isotope of higher mass receives the higher priority.

H 3 > H2 > H1
1 1 1
Rule 2: Multiple bonds

• If a double or a triple bond is linked to

chiral centre, the involved electrons are
duplicated or triplicated respectively.
Rule 3:

• Least priority group/atom always

away from the observer

• Working in 3-D, rotate the molecule

so that the lowest priority group is in
back
 How to assign R and S

• Clockwise direction = R
• Anti clockwise direction = S

R S
I) II)

III) IV)
Configuration in Cyclic Compounds
Naming from the Fischer Projection
R, S- Configuration in allenes, spiranes and biphenyls
 1.Assign group priority

The horizontal lines represent the bonds point out of the

2.If the lowest priority group (#4 group) is on
plane, and the vertical lines represent the bonds that point
a vertical bond, determine the priority decrease
behind the plane.
direction from #1→#2→#3 as usual to get the
configuration, clockwise is R and counterclockwise is S.
3.If the lowest priority group is on a horizontal bond (as the case
in the following structure), determine the priority decrease direction
as in step 2, then reverse the answer to opposite way, to get
the final configuration.
Properties of Fisher projection:
2. Rotate the Fisher projection 180º get same structure,
1. One switch (interchange) of two
with the configuration retained.
groups in a Fisher projection invert the
configuration, two switches bring the
original isomer back.

3. Rotate the Fisher projection 90º get the configuration

inverted.