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Chapter 5
Stereochemistry
References:
1. Title: Organic Chemistry (fifth edition)
Author: Paula Yurkanis Bruice
Publisher: Pearson International Edition
2. Title: Stereokimia
Author: Poh Bo Long
Publisher: Penerbit Universiti Sains Malaysia
3. Stereochemistry
Cik Rabiah Bee Abdul Carim
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Stereochemistry• Recall that stereochemistry refers to the three-dimensional
structure of a molecule.
• As a consequence of stereochemistry, apparently minor
differences in 3-D structure can result in vastly different
properties. We can observe this by considering starch and cellulose, which are both composed of the same repeating
unit.
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Figure 5.1:Three-dimensional structure of cellulose and starch
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• Recall that isomers are different compounds with the same molecular formula.
• The two major classes of isomers are constitutionalisomers and stereoisomers.
Constitutional/structural isomers have different IUPAC names, the same or different functional groups, different physical properties and different chemical properties.
Stereoisomers differ only in the way the atoms are oriented in space. They have identical IUPAC names (except for a prefix like cis or trans). They always have the same functional group(s).
• A particular three-dimensional arrangement is called a configuration. Stereoisomers differ in configuration.
The Two Major Classes of Isomers
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Figure 5.2: A comparison of constitutional isomers and stereoisomers.
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Classify each pair of compounds as
constitutional isomers or stereoisomers
CH3 CH3
CH3
CH3
CH3 CH3
CH3CH3
and
(a)
Oand
OH(b)
(c) CH3
CH3
and
CH3
CH3
(d)CH3
CH3
and
CH3
CH3
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• Although everything has a mirror image, mirror images may or may not be superimposable.
• Some molecules are like hands. Left and right hands are mirror images, but they are not identical, or superimposable.
Chiral and Achiral Molecules
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• Other molecules are like socks. Two socks from a pair are mirror images that
are superimposable. A sock and its mirror image are
identical.
• A molecule or object that is superimposable on its
mirror image is said to be achiral.
• A molecule or object that is not superimposable on its
mirror image is said to be chiral.
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• Consider several molecules to determine whether or not they are chiral.
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• The molecule labeled A and its mirror image labeled B are not superimposable. No matter how you rotate A and B, all the atoms never align. Thus, CHBrClF is
a chiral molecule, and A and B are different compounds.
• A and B are stereoisomers—specifically, they are
enantiomers.
• A carbon atom with four different groups is a tetrahedral stereogenic center.
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• In general, a molecule with no stereogenic centers will not be chiral. There are exceptions to this that will be considered in Chapter 17.
• With one stereogenic center, a molecule will always
be chiral.
• With two or more stereogenic centers, a molecule may or may not be chiral.
• Achiral molecules usually contain a plane of
symmetry but chiral molecules do not.
• A plane of symmetry is a mirror plane that cuts the molecule in half, so that one half of the molecule is
a reflection of the other half.
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Summary of the Basic Principles of Chirality:
• Everything has a mirror image. The fundamental question is whether the molecule and its mirror image are superimposable.
• If a molecule and its mirror image are not
superimposable, the molecule and its mirror image are chiral.
• The terms stereogenic center and chiral molecule
are related but distinct. In general, a chiral molecule must have one or more stereogenic centers.
• The presence of a plane of symmetry makes a
molecule achiral.
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• To locate a stereogenic center, examine each
tetrahedral carbon atom in a molecule, and look at the
four groups—not the four atoms—bonded to it.
• Always omit from consideration all C atoms that
cannot be tetrahedral stereogenic centers. These
include
CH2 and CH3 groups
Any sp or sp2 hybridized C
Stereogenic Centers (Stereocenters)
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• Any atom at which the interchange of
two groups gives a stereoisomer.
• Examples:• Asymmetric or chiral C atoms, often designated by
an asterisk(*)
• Double-bonded carbons in cis-trans isomers
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Chiral Carbons
• Tetrahedral carbons with 4 different attached
groups are chiral.
• If there’s only one chiral carbon in a molecule, its
mirror image (spatial arrangements) will be a
different compound (enantiomer).
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• Larger organic molecules can have two, three or
even hundreds of stereogenic centers.
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To draw both enantiomers of a chiral compound such as
2-butanol, use the typical convention for depicting
a tetrahedron:
(i) place two bonds in the plane, one in front of the plane
on a wedge, and one behind the plane on a dash.
(ii) Then, to form the first enantiomer, arbitrarily place the
four groups—H, OH, CH3 and CH2CH3—on any bond to
the stereogenic center. Then draw the mirror image.
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Figure 5.3:Three-dimensional representations for pairs of enantiomers
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• Stereogenic centers may also occur at carbon atoms that are part of a ring.
• To find stereogenic centers on ring carbons, always draw the rings as flat polygons, and look for
tetrahedral carbons that are bonded to four different groups.
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• In 3-methylcyclohexene, the CH3 and H substituents that are above and below the plane of the ring are drawn with wedges and dashes as usual.
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• Many biologically active molecules contain stereogenic centers at ring carbons.
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• Since enantiomers are two different compounds, they
need to be distinguished by name. This is done by
adding the prefix R or S to the IUPAC name of the
enantiomer.
• Naming enantiomers with the prefixes R or S is called
the Cahn-Ingold-Prelog system.
Labeling Stereogenic Centers with R or S
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Carl-Ingold –Prelog Convention
(Perspective drawing)
• Assign a priority number to each group
attached to the chiral carbon.
• Atom with highest atomic number assigned
the highest priority #1.
• The heavier isotopes have higher priorities
with different isotopes of the same element.
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• If two atoms on a stereogenic center are the same, assign priority based on the atomic number of the atoms bonded to these atoms. One atom of higher
atomic number determines the higher priority.
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• If two isotopes are bonded to the stereogenic center, assign priorities in order of decreasing mass number. Thus, in comparing the three isotopes of
hydrogen, the order of priorities is:
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Labeling Stereogenic Centers with R or S
Figure 5.4: Examples of assigning priorities to stereogenic centers.
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• To assign a priority to an atom that is part of a multiple bond, treat a multiply bonded atom as an equivalent number of singly bonded atoms. For example, the C of a C=O is considered to be bonded to two O atoms.
• Other common multiple bonds are drawn below:
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• Double and triple bonds are treated like
each were a bond to a separate atom.
O
CH3
CH3
O
CH3
CH3
(O) (C)
CH3
CH3 CH3
CH3CH3
CH3
(C)
CH3
(C)
CH3
CH N N
(N)
H
(N) (C)
(C)
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• In case of ties, look at the next atoms along
the chain.
CH2Cl
HOH2C
OH
H
3
2
4
1
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Figure 5.5: Examples: Orienting the lowest priority group in back.
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• When drawing the arrows from group 1 to group 2 , one can draw past the group with the lowest priority(4), but never draw past the group with the next lowest priority(3).
H
OH
H3CH2C
CH2CH2Br
1
4
2
3 H
OH
H3CH2C
CH2CH2Br
1
4
2
3
CH2Cl
HOH2C
OH
H
3
2
4
1
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H
HOOC
CH3NH21
2
3 4CH3
COOH
HNH2
2
1
34
H
Cl
Br
F
CH3 CH3
OHCH2Cl
HOOC
OHH
CH2OH
CHO
OH
H
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• Interchanging any two groups inverts the configuration
of that asymmetryc carbon from (R) to (S) & vice versa.
H
H5C6
H3CH2CD
switch
D and HD
H5C6
H3CH2CH
1
2
3
4
1
2 3
4
CH2CH3
BrH2C
H3C
Cl
CH3
H
OH
CH2BrCH3 CH3
Cl
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Fischer Projections
• Flat drawing that represents a 3D 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.
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Fischer Rules
• Carbon chain is on the vertical line, usually
with the IUPAC numbering from top to
bottom.
• Highest oxidized carbon substituent at top.
• Rotation of 180° in plane does not change
the configuration of a molecule.
• Do not rotate 90°!
• Do not turn over out of plane!
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H
CH2OH
CH3
OH180
0
OH
CH3
CH2OH
H
CH3
Br H
H Br
CH3
1800
CH3
Br H
H Br
CH3
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Fischer (R) and (S)
CH2Br
(H3C)2HC
H3CH2C
CH3
H
Br
CH3
CH2CH3
H
H3CH2CH2C
OH
CH2OH
CHO
H OH
H OH
CH2OH
CH2OH
OH H
H OH
CH2OH
Cl
H
H3CH2C
CH3
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Fischer Mirror Images
• Easy to draw, easy to find enantiomers, easy to find internal mirror planes.
• Examples:
Br
Br
H
CH3
CH3
CH3
CH3
Br H
Br HH
σ σ
OH
CH3
CH3
Hσ
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• For a molecule with n stereogenic centers, the maximum
number of stereoisomers is 2n.
• Let us consider the stepwise procedure for finding all the
possible stereoisomers of 2,3-dibromopentane.
Diastereomers
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• After drawing the compound and the mirror image in the described manner, there are only to do two operations to see if the atoms align.
• Place B directly on top of A; and rotate B 180°and place it on top of A to see if the atoms align.
• Atoms of A and B do not align, making A and B
nonsuperimposable mirror images—i.e., enantiomers.
• A and B are two of the four possible stereoisomers of 2,3-
dibromopentane.
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• Switching the positions of H and Br (or any two groups) on one
stereogenic center of either A or B forms a new stereoisomer (labeled C in this example), which is different from A and B. The
mirror image of C is labeled D. C and D are enantiomers.
• Stereoisomers that are not mirror images of one another are
called diastereomers. For example, A and C are diastereomers.
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Figure 5.6: Summary: The four stereoisomers of 2,3-dibromopentane.
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• Consider the stereoisomers of 2,3-dibromobutane. Since this molecule has two stereogenic centers, the maximum number of stereoisomers is 4.
Meso Compounds
• To find all the stereoisomers of 2,3-dibromobutane, arbitrarily
add the H, Br, and CH3 groups to the stereogenic centers,
forming one stereoisomer A, and then draw its mirror image, B.
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• To find the other two stereoisomers (if they exist), switch the
position of two groups on one stereogenic center of one enantiomer only.
• Switching the positions of H and Br on one stereogenic center ofA forms C, which is different from both A and B.
• A meso compound is an achiral compound that contains
tetrahedral stereogenic centers. C is a meso compound.
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• Compound C contains a plane of symmetry, and is achiral.
• Meso compounds generally contain a plane of symmetryso that they possess two identical halves.
• Because one stereoisomer of 2,3-dibromobutane is superimposable on its mirror image, there are only three stereoisomers, not four.
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Figure 5.7 Summary: The three stereoisomers 2,3-dibromobutane.
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• When a compound has more than one stereogenic center, R and S configurations must be assigned to each of them.
R and S Assignments in Compounds with Two or More Stereogenic Centers.
One stereoisomer of 2,3-dibromopentane
The complete name is (2S,3R)-2,3-dibromopentane
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• Consider 1,3-dibromocyclopentane. Since it has two
stereogenic centers, it has a maximum of four stereoisomers.
Disubstituted Cycloalkanes
• A disubstituted cycloalkane can have two substituents on the
same side of the ring (cis isomer, A) or on opposite sides of
the ring (trans isomer, B). These compounds are
stereoisomers but not mirror images.
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• To find the other two stereoisomers (if they exist), draw the
mirror images of each compound and determine whether the
compound and its mirror image are superimposable.
• The cis isomer is superimposable on its mirror image, making
the images identical. Thus, A is an achiral meso compound.
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• The trans isomer is not superimposable on its mirror image,
labeled C, making B and C different compounds. B and C are
enantiomers.
• Because one stereoisomer of 1,3-dibromocyclopentane is
superimposable on its mirror image, there are only three
stereoisomers, not four.
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Stereochemistry
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Stereochemistry
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• The chemical and physical properties of two enantiomers are identical except in their interaction with chiral substances. They have identical physical properties, except for how they interact with plane-polarized light.
• Plane-polarized (polarized) light is light that has an electric vector that oscillates in a single plane. Plane-polarized light arises from passing ordinary light through a polarizer.
• A polarimeter is an instrument that allows polarized light to travel through a sample tube containing an organic compound. It permits the measurement of the degree to which an organic compound rotates plane-polarized light.
Physical Properties of Stereoisomers—Optical Activity
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• With achiral compounds, the light that exits the sample tube remains unchanged. A compound that does not change the plane of polarized light is said to be optically inactive.
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• With chiral compounds, the plane of the polarized light is
rotated through an angle αααα.
• The angle αααα is measured in degrees (°), and is called the observed rotation. A compound that rotates polarized light
is said to be optically active.
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• The rotation of polarized light can be clockwise or anticlockwise.
• If the rotation is clockwise (to the right of the noon position), the compound is called dextrorotatory. The rotation is labeled d or (+).
• If the rotation is counterclockwise, (to the left of noon), the compound is called levorotatory. The rotation is labeled l or (-).
• Two enantiomers rotate plane-polarized light to an equal extent but in opposite directions. Thus, if enantiomer A rotates polarized light +5°, the same concentration of enantiomer B rotates it –5°.
• No relationship exists between R and S prefixes and the (+) and (-) designations that indicate optical rotation.
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• An equal amount of two enantiomers is called a racemic
mixture or a racemate.
• A racemic mixture is optically inactive. Because two enantiomers rotate plane-polarized light to an equal extent
but in opposite directions, the rotations cancel, and no rotation is observed.
Racemic Mixtures
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• Specific rotation is a standardized physical constant for the
amount that a chiral compound rotates plane-polarized light.
• Specific rotation is denoted by the symbol [αααα] and
• defined using a specific sample tube length (l, in dm), concentration (c in g/mL), temperature (250C) and
wavelength (589 nm).
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Calculate [α]D
• A 1.00-g sample is dissolved in 20.0 mL
ethanol. 5.00 mL of this solution is placed
in a 20.0-cm polarimeter tube at 25°C.
The observed rotation is 1.25°
counterclockwise.
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• Enantiomeric excess (optical purity) is a measurement of how much one enantiomer is present in excess of the racemic mixture. It is denoted by the symbol ee.
Optical Purity
ee = % of one enantiomer - % of the other enantiomer.
• Consider the following example—If a mixture contains 75% of one enantiomer and 25% of the other, the enantiomeric excess is 75% - 25% = 50%. Thus, there is a 50% excess of one enantiomer over the racemic mixture.
• The enantiomeric excess can also be calculated if the
specific rotation [αααα] of a mixture and the specific rotation [αααα] of a pure enantiomer are known.
ee = ([αααα] mixture/[αααα] pure enantiomer) x 100.
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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°.
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• Since enantiomers have identical physical properties, they cannot be separated by common physical techniques like distillation.
• Diastereomers and constitutional isomers have different physicalproperties, and therefore can be separated by common physical techniques.
Figure 5.8: The physical properties of the three stereoisomers of tartaric acid.
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• Two enantiomers have exactly the same chemical properties exceptfor their reaction with chiral non-racemic reagents.
• Many drugs are chiral and often must react with a chiral receptor or chiral enzyme to be effective. One enantiomer of a drug may effectively treat a disease whereas its mirror image may be ineffective or toxic.
Chemical Properties of Enantiomers
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Enantiomers and the Sense of Smell
• Research suggests that the odor of a particular molecule is determined more by its shape than by the presence of a particular functional group.
• Because enantiomers interact with chiral smell receptors, some enantiomers have different odors.
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