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Definitions
Stereoisomers compounds with the same
connectivity, different arrangement in
space
Enantiomers stereoisomers that are nonsuperimposible mirror images; only
properties that differ are direction (+ or -)
of
optical rotation
Diastereomers stereoisomers that are not
mirror images; different compounds
with different physical properties
2013 Pearson Education, Inc.
More Definitions
Asymmetric center sp3 carbon with 4
different groups attached
Optical activity the ability to rotate the
plane of plane polarized light
Chiral compound a compound that is
optically active (achiral compound will not
rotate light)
Polarimeter device that measures the
optical rotation of the chiral compound
2013 Pearson Education, Inc.
Chirality
Chapter 5
Achiral
Mirror images that can be superposed
are achiral (not chiral).
Chapter 5
Stereoisomers
Enantiomers: Compounds that are
nonsuperimposable mirror images. Any molecule
that is chiral must have an enantiomer.
Chapter 5
Chapter 5
Stereocenters
An asymmetric carbon atom is the most
common example of a chirality center.
Chirality centers belong to an even broader
group called stereocenters. A stereocenter (or
stereogenic atom) is any atom at which the
interchange of two groups gives a stereoisomer.
Asymmetric carbons and the double-bonded
carbon atoms in cis-trans isomers are the most
common types of stereocenters.
Chapter 5
Chapter 5
Achiral Compounds
Chapter 5
11
Planes of Symmetry
Chapter 5
12
Chapter 5
13
Chapter 5
14
Chapter 5
15
CahnIngoldPrelog
Priority System
Enantiomers have different spatial arrangements of
the four groups attached to the asymmetric carbon.
The two possible spatial arrangements are called
configurations.
Each asymmetric carbon atom is assigned a letter (R)
or (S) based on its three-dimensional configuration.
CahnIngoldPrelog convention is the most widely
accepted system for naming the configurations of
chirality centers.
Chapter 5
16
Chapter 5
17
Assign Priorities
Atomic number:
Chapter 5
18
Chapter 5
19
Chapter 5
20
Chapter 5
21
Assign Priorities
Counterclockwise
(S)
Chapter 5
22
Example
3
CH2CH3
OH
rotate
CH2CH3
CH3CH2CH2
4
CH3CH2CH2
H
OH
1
Clockwise
(R)
When rotating to put the lowest priority group in the back,
keep one group in place and rotate the other three.
2013 Pearson Education, Inc.
Chapter 5
23
Example (Continued)
3
CH3
1
H4
CH3CH2CH=CH
CH2CH2CH2CH3
2
Counterclockwise
(S)
Chapter 5
24
Configuration in Cyclic
Compounds
Chapter 5
25
Properties of Enantiomers
Same boiling point, melting point, and density.
Same refractive index.
Rotate the plane of polarized light in the same
magnitude, but in opposite directions.
Different interaction with other chiral molecules:
Active site of enzymes is selective for a specific
enantiomer.
Taste buds and scent receptors are also chiral.
Enantiomers may have different smells.
Chapter 5
26
Polarized Light
Plane-polarized light is composed of
waves that vibrate in only one plane.
Chapter 5
27
Optical Activity
Enantiomers rotate the plane of polarized
light in opposite directions, but same number
of degrees.
Chapter 5
28
Polarimeter
Clockwise
Counterclockwise
Dextrorotatory (+)
Levorotatory (-)
Chapter 5
29
Specific Rotation
Observed rotation depends on the length
of the cell and concentration, as well as
the strength of optical activity, temperature,
and wavelength of light.
[] = (observed)
c l
Where (observed) is the rotation observed in the
polarimeter, c is concentration in g/mL, and l is
length of sample cell in decimeters.
2013 Pearson Education, Inc.
Chapter 5
30
Solved Problem 2
Whenoneoftheenantiomersof2butanolisplacedinapolarimeter,theobservedrotationis4.05
counterclockwise.Thesolutionwasmadebydiluting6gof2butanoltoatotalof40mL,andthe
solutionwasplacedintoa200mmpolarimetertubeforthemeasurement.Determinethespecific
rotationforthisenantiomerof2butanol.
Solution
Sinceitislevorotatory,thismustbe()2butanolTheconcentrationis6gper40mL=0.15g/mL,and
thepathlengthis200mm=2dm.Thespecificrotationis
[] 25
=
D
4.05
(0.15)(2)
Chapter 5
=13.5
31
Biological Discrimination
Chapter 5
32
Biological Activity
(R)(+) Thalidomide
O O
N
H
N
O
a sedative and hypnotic
(S)(-) Thalidomide
O
a teratogen
H
N
O
N(CH3)2
(+/-) Celexa
(-) Lexapro
F
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Racemic Mixtures
Chapter 5
35
Racemic Products
If optically inactive reagents combine to
form a chiral molecule, a racemic mixture
is formed.
Chapter 5
36
Optical Purity
Optical purity (o.p.) is sometimes called
enantiomeric excess (e.e.).
One enantiomer is present in greater
amounts.
o.p. =
observed rotation
rotation of pure enantiomer
Chapter 5
X 100
37
Calculate % Composition
The specific rotation of (S)-2-iodobutane is +15.90.
Determine the % composition of a mixture of (R)and (S)-2-iodobutane if the specific rotation of the
mixture is -3.18.
Sign is from the enantiomer in excess: levorotatory.
o.p. =
3.18
15.90
2l = 120%
2013 Pearson Education, Inc.
X 100 = 20%
l = 60%
Chapter 5
d = 40%
38
Chirality of Conformers
If equilibrium exists between two chiral
conformers, the molecule is not chiral.
Judge chirality by looking at the most
symmetrical conformer.
Cyclohexane can be considered to be
planar, on average.
Chapter 5
39
Chirality of Conformational
Isomers
Chapter 5
40
Nonmobile Conformers
Chapter 5
41
H
Cl
H
C
C
CH3
CH3
H
Cl
Penta-2,3-diene Is Chiral
Chapter 5
43
Fischer Projections
Flat representation of a 3-D molecule.
A chiral carbon is at the intersection of horizontal
and vertical lines.
Horizontal lines are forward, out of plane.
Vertical lines are behind the plane.
Chapter 5
44
Chapter 5
45
Fischer Rules
Carbon chain is on the vertical line.
Highest oxidized carbon is at top.
Rotation of 180 in plane doesnt
change molecule.
Rotation of 90 is NOT allowed.
Chapter 5
46
180 Rotation
Chapter 5
47
90 Rotation
Chapter 5
48
Glyceraldehyde
The arrow from group 1 to group 2 to group 3
appears counterclockwise in the Fischer projection.
If the molecule is turned over so the hydrogen is in
back, the arrow is clockwise, so this is the (R)
enantiomer of glyceraldehyde.
Chapter 5
49
Chapter 5
50
Cl
Cl
H
CH3
Chapter 5
51
(S)
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Cl
Cl
(S)
CH3
Chapter 5
52
Racemic Mixture
R,R
S,S
CO2H
CO2H
H
OH
HO
H
CO2H
HO
OH
CO2H
m.p. C
[] (degrees)
(g/mL)
2013 Pearson Education, Inc.
0
1.7723
Meso Compound
Internal Plane of Symmetry
Optically Inactive
R,S
CO2H
mirror
plane
S,R
CO2H
OH
HO
OH
HO
H
CO2H
CO2H
superimposible
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rotate 180
Diastereomers: Cis-trans
Isomerism on Double Bonds
These stereoisomers are not mirror
images of each other, so they are not
enantiomers. They are diastereomers.
Chapter 5
55
Diastereomers: Cis-trans
Isomerism on Rings
Cis-trans isomers are not mirror images, so
these are diastereomers.
Chapter 5
56
Diastereomers
Molecules with two or more chiral carbons.
Stereoisomers that are not mirror images.
Chapter 5
57
Chapter 5
58
2,3,4-trichlorohexane
How many stereoisomers?
Cl
* *
Cl
Cl
3 asymmetric centers
2n, n= # asymmetric centers (3)
8 stereoisomers
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n = 3; 2n = 8
CH3
CH3
CH3
CH3
S H
Cl
Cl
H R
Cl
Cl
S H
Cl
Cl
H R
Cl
Cl
RH
Cl
Cl
H S
Cl
CH2CH3
CH2CH3
CH2CH3
CH2CH3
CH3
CH3
CH3
CH3
Cl
Cl
Cl
CH2CH3
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
CH2CH3
CH2CH3
Cl
CH2CH3
A Carbohydrate
CHO
OH
OH
OH
H
HO
CH2OH
(+) D-Glucose
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Meso Compounds
Chapter 5
62
Number of Stereoisomers
Chapter 5
63
Properties of Diastereomers
Diastereomers have different physical
properties, so they can be easily separated.
Enantiomers differ only in reaction with other
chiral molecules and the direction in which
polarized light is rotated.
Enantiomers are difficult to separate.
Convert enantiomers into diastereomers to be
able to separate them.
Chapter 5
64
Chemical Resolution of
Enantiomers
Chapter 5
65
Chapter 5
66