Chapter 5 Stereoisomerism New

Chapter 5: Stereoisomerism
Stereoisomers are compounds that have the same structural

formula in terms of order of attachment, but differ in
arrangements of the atoms in space.
The difference in odor between caraway seeds and mint leaves arises from two
stereoisomers of carvone due to different arrangement of atoms at the carbon (*)
5.1 Chirality and Enantiomers
• A molecule (or object) is either chiral or achiral. The word chiral,

pronounced “kairal” to rhyme with spiral, comes from the Greek (cheir,
hand). A chiral molecule (or object) is one that exhibits the property of
handedness. An achiral molecule does not have this property.
• What test can we apply to tell whether a molecule (or object) is chiral or
achiral?
• We examine the molecule (or object) and its mirror image. The mirror
image of a chiral molecule cannot be superimposed on the molecule itself.
The mirror image of an achiral molecule, however, is identical to or
superimposable on the molecule itself.
Mirror-image relationship of chiral and achiral objects
Stereoisomers have the same order of attachment of atoms but
different
spatial arrangements of atoms.
Chiral molecules possess the property of handedness.
Achiral molecules do not possess the property of handedness.
Enantiomers are a pair of molecules related as nonsuperimposable

mirror images.
4.2 Stereogenic Centers: the Stereogenic Carbon Atom
Carbon atoms with four different groups attached to them are

called stereogenic carbon atoms (also called chiral carbon)
More general case for stereogenic center
Plane of symmetry (sometimes called a mirror plane) is a plane that
passes through a molecule (or object) in such a way that what is on one
side of the plane is the exact reflection of what is on the other side. Any
molecule with a plane of symmetry is achiral. Chiral molecules do not
have a plane of symmetry
How many stereogenic carbons does 3-methylhexane have?
Draw the two enantiomers of 3-methylhexane.?

PROBLEM 5.2 Find the stereogenic centers in
a.CH3CH2CHBrCH2CH2CH2CH3
b. 3-methylcyclohexene
c. ClFCHCH3
d. 2,3-dibromobutane
PROBLEM 5.3 Which of the following compounds is chiral?
a. 1-bromo-1-phenylethane b. 1-bromo-2-phenylethane
4.3 Configuration and the R-S Convention
Enantiomers differ in the arrangement of the groups attached to

the stereogenic center. This arrangement of groups is called the
configuration of the stereogenic center. Enantiomers are another
type of configurational isomer; they are said to have opposite
configurations.
R-S or Cahn–Ingold–Prelog System
The priority order of the four groups is set in the following way:
Rule 1
The atoms directly attached to the stereogenic center are
ranked according to atomic number. The higher the atomic
number, the higher the priority
Rule 2
If a decision cannot be reached with rule 1, work outward from
the stereogenic center until a decision is made. Example of
ethyl and methyl below.
PROBLEM 5.8 Assign a priority order to each of the following sets of groups:
a. -CH(CH3)2, -CH3, -H, -NH2

b. -OH, -Br, -CH3, -CH2OH
c. -OCH3, -NH(CH3)2, -CH2NH2, -OH
d. -CH2CH2CH3, -CH2CH3, -C(CH3)3, -CH(CH3)2
For stereogenic centers in cyclic compounds, the same rule for assigning
priorities is followed
Rule 3
Multiple bonds are treated as if they were an equal number of
single bonds.
Which group has the higher priority, isopropyl or vinyl?
Assign the configuration (R or S) to the following enantiomer of
3-methylhexane
Now view the molecule from the side opposite the lowest-
priority group (-H) and determine whether the remaining
three groups, from high to low priority, form a clockwise (R) or
counterclockwise (S) array.
What is absolute configuration for each of the stereogenic
center shown in the following compounds?
5.4 The E-Z convention for Cis-Trans Isomers
Assign the priorities of the two groups attached to each carbon of the
double bond:
If the two higher-priority groups are on opposite sides of the double bond,
the prefix E (from the German entgegen, opposite) is used.
If the two higher-priority groups are on the same side of the double bond,
the prefix is Z (from the German zusammen, together).
Name each compound by the E-Z system
( E ) -2-pentene ( E ) -1-bromo-2-chloro-1-fluoroethene
Write the structure for
a. (E)-1,3-hexadiene
b. b. (Z)-2-butene
5.5 Polarized Light and Optical Activity
An ordinary light beam consists of waves that vibrate in all

possible planes perpendicular to its path. However, if this light
beam is passed through certain types of substances, the
waves of the transmitted beam will all vibrate in parallel
planes.
A polarimeter is an instrument used to detect optical activity.
An optically active substance rotates plane-polarized light, whereas an
optically inactive substance does not.
• The angle through which the analyzer prism must be
rotated in this experiment is called α, the observed
rotation. It is equal to the number of degrees that the
• optically active substance rotated the beam of plane-
polarized light. If the analyzer must be rotated to the right
(clockwise), the optically active substance is said to
be dextrorotatory (+); if rotated to the left
(counterclockwise), the substance is levorotatory (-)
Example
Camphor is optically active. A camphor sample (1.5g) dissolved
in ethanol (optically inactive) to a total volume of 50 mL, placed in
a 5-cm polarimeter sample tube, gives an observed rotation of
+0.660 at 200C (using the sodium D-line). Calculate and express
the specific rotation of camphor.
5.6 Properties of Enantiomers
Enantiomers have identical achiral properties, such as

melting point, boiling point, density, and various types of
spectra. Their solubilities in an ordinary, achiral solvent
are also identical. However, enantiomers have different
chiral properties, one of which is the direction in which
they rotate plane-polarized light (clockwise or
counterclockwise).
5.7 Fischer Projection Formulas
A Fischer projection is a type of two-dimensional formula

of a molecule used to represent the three-dimensional
configurations of stereogenic centers.
There are two important things to notice about Fischer projection formulas.
First, the C for the stereogenic carbon atom is omitted and is represented
simply as the crossing point of the horizontal and vertical lines.
Second, horizontal lines connect the stereogenic center to groups that project
above the plane of the page, toward the viewer; vertical lines lead to groups
that project below the plane of the page, away from the viewer.
Determine the absolute (R or S) configuration of the stereoisomer of
2-chlorobutane shown in the following Fischer projection
Determine the absolute configuration of the following enantiomer of 2-
butanol from its Fischer projection
5.8 Compounds with More Than One Stereogenic
Center; Diastereomers.
It is important to be able to determine how many

isomers exist and how they are related to one another.
n chiral centers give rise to 2n possible stereoisomers.

The four stereoisomers of 2-bromo-3-chlorobutane a compound
with two stereogenic centers
Consider the relationship between, for example, the
(2R,3R) and (2R,3S) forms of the isomers .These forms
are not mirror images because they have the same
configuration at carbon-2, though they have opposite
configurations at carbon-3.
They are certainly stereoisomers, but they are not
enantiomers. For such pairs of stereoisomers, we use the
term diastereomers.
Diastereomers are stereoisomers that are not mirror

images of each other.
Given is the Fischer projection of glucose (blood sugar), how may
stereoisomers of this sugar are possible?
5.9 Meso Compounds; the Stereoisomers of Tartaric Acid
Consider the stereoisomers of 2,3-dichlorobutane

.
The “two” structures, (R,S) and (S,R), in fact, now represent a single compound
A meso compound is an
achiral diastereomer of a
compound with
stereogenic centers
A racemic mixture is a 50:50
mixture of a pair of enantiomers.
Optically inactive
Achiral Mixture

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Chapter 5: Stereoisomerism

Stereoisomers are compounds that have the same structural

• A molecule (or object) is either chiral or achiral. The word chiral,

Chiral molecules possess the property of handedness.

Achiral molecules do not possess the property of handedness.

Enantiomers are a pair of molecules related as nonsuperimposable

Carbon atoms with four different groups attached to them are

Draw the two enantiomers of 3-methylhexane.?

Enantiomers differ in the arrangement of the groups attached to

a. -CH(CH3)2, -CH3, -H, -NH2

An ordinary light beam consists of waves that vibrate in all

Enantiomers have identical achiral properties, such as

A Fischer projection is a type of two-dimensional formula

It is important to be able to determine how many

n chiral centers give rise to 2n possible stereoisomers.

Diastereomers are stereoisomers that are not mirror

Consider the stereoisomers of 2,3-dichlorobutane

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