STEREOCHEMISTRY AT TETRAHEDRAL CENTERS

Handedness arises as a result

of the stereochemistry at
tetrahedral centers.
Identical molecules are
superimposable.
An object or molecule that is
not superimposable on its mirror
image is said to be chiral
(handed).

STEREOCHEMISTRY AT TETRAHEDRAL CENTERS

A chiral molecule do not have a plane of symmetry

cutting through it so that one half is a mirror image of the
other half.
Non chiral or achiral has plane of symmetry and are
identical to its mirror image.

STEREOCHEMISTRY AT TETRAHEDRAL CENTERS

Chiral center, stereocenter, asymmetric center or

stereogenic center
are terms used to describe
tetrahedral center bounded to four different groups.
Molecules with n chirality center can have a
maximum of 2n stereoisomers.
Are these molecules chiral or achiral? Identify all
the stereogenic centers if any

Optical Activity
Optical activity is the ability to rotate plane polarized light.
Those that
rotate plane
polarized
light are said
to be
optically
active

Optical Activity
[]D =
=

observed rotation (degrees)

Pathlength, l (dm) x Concentration, c (g/cm3)

lxc

Specific rotation is a physical constant characteristics of

a given optically active compound.
Example:
(+)-lactic acid has []D = +3.82 and (-)-lactic acid has []D = -3.82. This means
that the two enantiomers rotate plane polarized light to exactly the same extent
but in opposite directions.

Enantiomers
Enantiomers are pair of non superimposable mirror image.

Enantiomers are identical in all physical properties except for

their optical activity.
The stereochemical configuration of a chirality center can be
specified as either R (Rectus) or S (Sinister)
X-ray diffraction is currently employed to determine the
configuration at chirality center.

Sequence Rule for Specifying Configuration

Sequence Rule for Specifying Configuration

Sequence Rule for Specifying Configuration

Assign R or S configuration

Diastereomers
Diastereomers are stereosomers that are not mirror images.
Diastereosomers can have quite different physical and chemical properties
from one another.
Epimers are diastereomers that differ in configuration at only one chirality
center.
i. Identify the chirality centers in these
molecules
ii. .Assign correct R or S configuration to
each chirality center.
iii. . What is the relationship between A &
B ; C &D

Meso Compounds
Meso compounds contains chirality centers but are achiral overall
Meso compounds have a plane of symmetry .

identic
al
Plane of symmetry
through the C2-C3
making the one half of
the molecule a mirror
image of the other half.

Racemic Mixtures & Resolution

Racemic mixtures or Racemates are 50:50 mixtures of (+) and
(-) enantiomers. i.e () or d,l.
Racemic is a solution in which both enantiomers of a
compound are present in equal amounts.
Racemic shows no optical activity.
Racemates and individual diastereomers differ in their
physical properties such as solubility, melting point, and
boiling point.

Racemic Mixtures & Resolution

Resolution : is a technique employ to separate racemic mixtures.
Example
By employing chiral reagent.
These salts are
diastereomers, therefore
have different chemical
and physical properties
and it may be possible
to separate them by
crystallization or by
other means.

Prochiral
A molecule is prochiral if it can be converted from achiral to chiral in a
single chemical step.

Which enantiomer of the product observed depend on

which face of the planar carbonyl group undergoes
reaction.

Prochiral
An sp3 hybridized atom is said to be a prochirality center
if, by changing one of its attached groups, it becomes a
chiral center.

Chiral Drug
Penicillin V
Is antibiotic
Isolated from penicillium mold
Is chiral
Its enantiomer has no antibiotic
activity.

Homework

5.2 (a,b) , 5.3, 5.6, 5.7, 5.8(a,b), 5.10(a,b,c), 5.11, 5.15,

5.16(a,b,c), 5.27, 5.32(a,b,c), 5.37, 5.38, 5.43, 5.46, 5.47(a),
5.63