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STEREOCHEMISTRY
TYPES OF ISOMERS

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The part of science which deals with structure in three

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dimensions is called Stereochemistry

Isomers which have the different orientations of atoms in

space are called stereoisomer

The arrangements of atoms in space that characterizes a

Particular stereoisomer is called configuration

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 Molecular Chirality:
Enantiomers

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CHIRALITY

A molecule is chiral if its two mirror image

forms are not superposable upon one another.
ASYMMETRIC!

A molecule is achiral if its two mirror image

forms are superposable. SYMMETRIC!

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BROMOCHLOROFLUOROMETHANE IS CHIRAL

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Cl It cannot be superposed point for
Br point on its mirror image.
H

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 Babi K Kafle
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CHIRALITY
BROMOCHLOROFLUOROMETHANE IS CHIRAL

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Cl Cl
Br Br
H H

F F
To show nonsuperposability, rotate
this model 180° around a vertical axis.
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BROMOCHLOROFLUOROMETHANE IS CHIRAL

Cl Br
Br Cl
H H

F F

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ANOTHER LOOK

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 ENANTIOMERS

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nonsuperposable mirror images are
called enantiomers

and

are enantiomers with respect to each other

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CHLORODIFLUOROMET

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HANE
IS ACHIRAL
Mirror

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 CHLORODIFLUOROMET
HANE
IS ACHIRAL

The two
structures are
mirror images,
but are not
enantiomers,
because they
can be
superposed on
each other.
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 THE CHIRALITY CENTER

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 THE CHIRALITY CENTER

a carbon atom with four

w different groups attached to it

x C y also called:
chiral center or,
z
asymmetric center or,
stereocenter or,
stereogenic center

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 CHIRALITY AND CHIRALITY
CENTERS
A molecule with a single chirality center
is chiral.

Bromochlorofluoromethane is an example.

Chirality center H

Cl C F

Br 15

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CHIRALITY AND CHIRALITY CENTERS

A molecule with a single chirality center

is chiral.

2-Butanol is another example.

CH3 C CH2CH3

OH 15

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 EXAMPLES OF MOLECULES WITH 1 CHIRALITY
CENTER

CH3

CH3CH2CH2 C CH2CH2CH2CH3

CH2CH3

a chiral alkane
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 EXAMPLES OF MOLECULES WITH 1 CHIRALITY
CENTER

OH

Linalool, a naturally occurring chiral alcohol

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EXAMPLES OF MOLECULES WITH 1 CHIRALITY
CENTER
H2C CHCH3

O
1,2-Epoxypropane: a chirality center
can be part of a ring
attached to the chirality center are:
—H
—CH3
—OCH2
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—CH2O
 EXAMPLES OF MOLECULES WITH 1 CHIRALITY
CENTER

Limonene: a chirality
CH3
center can be part of a
ring
Chiral center
attached to the
chirality center are:
—H
H C CH2 —CH2CH2

CH3 —CH2CH=C
—C=C 20

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 EXAMPLES OF MOLECULES WITH 1 CHIRALITY
CENTER

D C CH3

Chiral as a result of isotopic substitution

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 A MOLECULE WITH A SINGLE CHIRALITY
CENTER
MUST BE CHIRAL.
But, a molecule with two or more
chirality centers may be chiral
or it may not

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 Symmetry in Achiral
Structures

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 PLANE OF SYMMETRY

F C F

Cl

A plane of symmetry bisects a molecule into two

mirror image halves. Chlorodifluoromethane
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has a plane of symmetry.
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 PLANE OF SYMMETRY

A plane of symmetry bisects a molecule into two

mirror image halves.
1-Bromo-1-chloro-2-fluoroethene has a plane 26

of symmetry.
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PROPERTIES OF CHIRAL MOLECULES:
OPTICAL ACTIVITY

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 OPTICAL ACTIVITY

A substance is optically active if it rotates

the plane of polarized light.

In order for a substance to exhibit optical

activity, it must be chiral and one enantiomer
must be present in excess of the other.

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 LIGHT

has wave properties

periodic increase and decrease in amplitude of wave
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 LIGHT

optical activity is usually measured using light having a

wavelength of 589 nm this is the wavelength of the yellow light
from a sodium lamp and is called the D line of sodium
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 POLARIZED
LIGHT
ordinary
(nonpolarized)
light consists of
many beams
vibrating in
different planes

plane-polarized
light consists of
only those beams
that vibrate in the
same plane
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 POLARIZATION OF LIGHT

Nicol prism
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 PLANE-POLARIZED LIGHT
 The light made-up of only one type of electromagnetic
wave that oscillate in one plane after passing through a
polarizer.

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 ROTATION OF PLANE-POLARIZED
LIGHT

Sample 

Light Analyzer
Source

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SPECIFIC ROTATION

Where  (observed) is the rotation observed in the

polarimeter, c is concentration in g/mL, and l is length
of sample cell in decimeters.

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 Solved Problem
When one of the enantiomers of 2-butanol is placed in a polarimeter, the observed rotation is 4.05°
counterclockwise. The solution was made by diluting 6 g of 2-butanol to a total of 40 mL, and the
solution was placed into a 200-mm polarimeter tube for the measurement. Determine the specific
rotation for this enantiomer of 2-butanol.

Solution
Since it is levorotatory, this must be (–)-2-butanol The concentration is 6 g per 40 mL = 0.15 g/mL, and
the path length is 200 mm = 2 dm. The specific rotation is

– 4.05°
[] 25 = = –13.5°
D (0.15)(2)

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DIRECTION OF ROTATION

Levorotatory – optically active molecules

that rotate the plane of polarization to the left or
counterclockwise
Dextrorotatory - optically active molecules
that rotate the plane of polarization to the right or
clockwise

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FURTHER INFORMATION

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 https://www.khanacademy.org/test-prep/mcat/chemical-processes
/stereochemistry/a/chiral-drugs

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ENANTIOMERS
 Sterioisomers which nonsuperposable mirror images of
each other are called enantiomers
 They rotates plane-polarized light in opposite direction but
with equal magnitude
 They have identical physical properties like melting point,
boiling point, relative density etc.
 They have identical chemical properties except towards
optically active reagents

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EXAMPLES

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 RACEMIC MIXTURE OR RACEMIC MODIFICATION
OR RACEMATES
a mixture containing equal quantities

of enantiomers is called a racemic mixture and

specified by prefix (dl) or ( )

a racemic mixture is optically inactive ( = 0)

a sample that is optically inactive can be

either an achiral substance or a racemic

mixture
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 OPTICAL
PURITY
an optically pure substance consists exclusively

of a single enantiomer

enantiomeric excess =

% one enantiomer – % other enantiomer

% optical purity = enantiomeric excess

e.g. 75% (-) – 25% (+) = 50% opt. pure (-)

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 ABSOLUTE
AND
RELATIVE CONFIGURATION

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CONFIGURATION

The arrangement of atoms that characterizes

a particular stereoisomer is called configuration

Relative configuration compares the

arrangement of atoms in space of one compound
with those of another.
until the 1950s, all configurations were relative

Absolute configuration is the precise arrangement

of atoms in space.
we can now determine the absolute
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configuration of almost any compound
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 RELATIVE
CONFIGURATION
H2, Pd
CH3CHCH CH2 CH3CHCH2CH3

OH OH
[] + 33.2° [] + 13.5°

No bonds are made or broken at the stereogenic center

in this experiment. Therefore, when (+)-3-buten-2-ol
and (+)-2-butanol have the same sign of rotation, the
arrangement of atoms in space is analogous. The two
have the same relative configuration.
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Babi K Kafle
 RELATIVE
CONFIGURATION
HBr
CH3CH2CHCH2OH CH3CH2CHCH2Br

CH3 CH3
[] -5.8° [] + 4.0°

Not all compounds that have the same relative

configuration have the same sign of rotation. No bonds
are made or broken at the stereogenic center in the
reaction shown, so the relative positions of the atoms
are the same. Yet the sign of rotation changes.
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Babi K Kafle
 SEQUENCE RULES FOR SPECIFICATION
CONFIGURATION

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 The Cahn-Ingold-Prelog
or
R-S
System
or
Sequence rule

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Babi K Kafle
 RULE 1
 Look at the four atoms directly attached to the chirality
center and assign priorities in order of decreasing atomic
number. The atom with the highest atomic number is
ranked first; the atom with lowest atomic number is
ranked fourth (usually hydrogen).
 For Isotopes ,the atom of higher mass number has higher
priority

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EXAMPLE…….

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Atomic number: F > N > C > H

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 RULE 2
 If a decision about priority can’t be reached by applying
Rule 1, compare atomic numbers of the second atoms in
each substituent, continuing as necessary through the
third or fourth atoms until the first point of difference is
reached.

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EXAMPLE…..

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 RULE 3
 Multiple bonds are equivalent to the same number of
single-bonded atoms.

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(R) AND (S) CONFIGURATION:
MULTIPLE BONDS

Treat double and triple

bonds as if each were a
bond to a separate atom.

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 ASSIGN PRIORITIES

Draw an arrow from Group 1 to Group 2 to Group 3 and back to

Group 1. Ignore Group 4.

Clockwise = (R) and Counterclockwise = (S)

R means right( rectus in Latin)

S means left( sinister in Latin)
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 RULES FOR CONFIGURATION
1) Orient the molecule so that the group of lowest
priority (4) is pointing directly opposite away from
an observer.
2) Look at the remaining three substituents, which
now radiate toward the observer. If a curved
arrow drawn from the highest to the second to
the third-highest priority substituent (1→2 →3) is
clockwise, we say that the chirality center has the
R configuration (Latin rectus, meaning “right”). If
an arrow from 1→2 →3 is counterclockwise, the
chirality center has the S configuration (Latin
sinister, meaning “left”). 56

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 H
EXAMPLE
Br C F

Cl

4 3

2
Order of decreasing rank:

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4>3>2 >1

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 EXAMPLE

1 1

4 3 3 4

2 2
Order of decreasing rank:
432

clockwise anticlockwise
R S 7-58

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 ENANTIOMERS OF 2-BUTANOL

H H
CH3CH2 CH2CH3
C OH HO C

H3C CH3

(S)-2-Butanol (R)-2-Butanol
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 VERY IMPORTANT!
Two different compounds with the
same sign of rotation need not have
the same configuration.

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https://www.youtube.com/watch?v=dpgq-cvZiAo
DIASTEREOMERS

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 Diastereomers are stereoisomers that are not related as
object and mirror image and are not enantiomers
 Diastereomers can have different physical properties
and reactivity. They have different melting points and
boiling points and different densities.
 They have two or more stereocenters.

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DIASTEREOMERS…….

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 Babi K Kafle
Enatiomers
I & II
III & IV

Diastereomers

I & III
I & IV
II & III
II & IV

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MESO COMPOUNDS

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 Dr. Wolf's CHM 201 & 202
GENERATION OF FIRST CHIRAL CENTRE

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GENERATION OF FIRST CHIRAL
CENTRE

Racemic modification/mixture
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MESO COMPOUNDS…

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A compound containg 2 or more
Chiral centers that is superimposable
with its mirror image is called
Meso compound

Meso compunds contain an internal

plane which divides the two halves
of the molecule wich are mirror
image
to each other
 Str III & IV are meso compounds
( both are same compound)
They are optically inactive 67
RESOLUTION OF RACEMIC MODIFICATION
Separation of racemic mixture into enantiomers……

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 Resolution of chiral acids through the formation of
diastereomeric salts requires adequate supplies of
suitable chiral bases. Brucine, strychnine, and quinine
frequently are used for this purpose because they are
readily available, naturally occurring chiral bases.
 Chiral acids, such as (+)-tartaric acid, (-)-malic acid, (-)-
mandelic acid, and (+)-camphor- 10-sulfonic acid, are
used for the resolution of a racemic base.

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RESOLUTION OF RACEMIC MODIFICATION

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Dr. Wolf's CHM 201 & 202
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 CONFORMATIONAL ANALYSIS OF
ETHANE

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a. Perspective formulas.  b. Newman Projections.  c. Andiron or
Sawhorse formulas 71
CONFORMATIONAL ISOMERISM OF ACYCLIC C-C
COMPOUNDS

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 The infinite number of different arrangements of atoms in space that is
a result of rotation about a single bond is called conformational
isomers, conformers or conformations.

 Another less common term is rotamers.

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 DIHEDRAL ANGLES
A dihedral angle or torsional angle (symbol: θ) is the angle

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between two bonds originating from different atoms in a Newman
projection

a.Dihedral angle  represented by a Andiron projection 

b represented by a Newman projection
 c  eclipsed and staggered conformations of ethane 7-73
ENERGY DIAGRAM FOR ROTATION ABOUT
THE CARBON–CARBON BOND IN ETHANE

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7-74
TORSIONAL ENERGY

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7-75
CONFORMATIONAL ANALYSIS OF PROPANE

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a Perspective formula. b Newman projection. c Andiron or
Sawhorse formula. (Staggered and Eclipsed conformations) 76
ENERGY DIAGRAM FOR ROTATION ABOUT THE
CARBON–CARBON BOND IN PROPANE

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CONFORMATIONAL ANALYSIS OF N-BUTANE

 a perspective formula. b Newman projection. c Andrion formula

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ENERGY DIAGRAM FOR N-BUTANE

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CYCLO ALKANES: BAEYER
STRAIN THEORY
 Baeyer’s theory is based upon some assumptions as following
1.All ring systems are planar. Deviation from normal tetrahedral angles results in to instable

CHEM 103
cycloalkanes.
2.The large ring systems involve negative strain hence do not exists.
3.The bond angles in cyclohexane and higher cycloalkanes (cycloheptane, cyclooctane,
cyclononane, etc.) are not larger than 109.50 because the carbon rings of those compounds
are not planar (flat) but they are puckered (Wrinkled).
Baeyer proposed “any deviation of bond angle from ideal bond angle value (109.50) will
produce a strain in molecule. Higher the deviation lesser the instability.

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HEAT OF COMBUSTION OF
CYCLOALKANES
-CH2- + O2 CO2 + H2O + Heat

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TYPES OF STRAIN
1.ANGLE STRAIN
 1.Angle strain is the increase in potential energy of a molecule
due to bond angles deviating from the ideal values.
 - Cyclic molecules are an excellent example to demonstrate
angular strain. An element that has a very large amount of
angle strain is cyclopropane. The carbons in cyclopropane want
to be in 109.5° angles with each other. However, due to the
geometry of the molecule, the carbons are forced into 60°
angles with each other. This causes severe strain in the
molecule..

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2.TORSIONAL STRAIN
 Torsional strain or eclipsing strain is the increase in potential
energy of a molecule due to repulsion between electrons in
bonds that do not share an atom.
 - When a molecule is able to rotate around a sigma bond, there
is bound to be different levels of torsional strain that vary with
the placements of the substituents relative to each other. This
leads to different conformations of molecules (such as
staggered or eclipsed) with different energy levels, which leads
to different levels of stability.
.

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3.STERIC STRAIN OR VAN-DER WALLS
STRAIN
 Steric strain can also be referred to as steric hindrance, which
is related to Van Der Waals repulsion, or the strain that occurs
as the distance between two atoms or substituents decreases.
Steric strain occurs when multiple substituent are close
together, and cannot be separated by rotation.
 - Steric strain is the increase in potential energy of a molecule
due to repulsion between electrons in atoms that are not
directly bonded to each other.

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CONFORMATIONS OF CYCLOHEXANE

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INTERCONVERSION (PUCKERED
STRUCTURE)
Confermers of Cyclohexane

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ENERGY DIAGRAM FOR CYCLOHEXANE

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CONFORMATIONS OF CYCLOHEXANE

 Chair conformation

a
b c
 Boat conformation

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a side-on perspective view,  b with hydrogens represented,
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 c Newman projection
 BOAT CONFORMATION..

Boat Twisted Boat

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 AXIAL AND EQUATORIAL BONDS

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 METHYLCYCLOHEXANE

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 Methylcyclohexane
….

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 CIS AND TRANS ISOMERS

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Cis and trans …..

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