Chapter-4 Stereochemistry
Chapter-4 Stereochemistry
Chapter-4 Stereochemistry
IV. Stereochemistry
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4.1 Isomerism: Constitutional Isomers and Stereoisomers
• Isomers are different compounds that have the same MF.
• Constitutional isomers are isomers that differ because their
atoms are connected in a different order.
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• Stereoisomers have their atoms connected in the same sequence
(the same constitution) but differ only in arrangement of their
atoms in space.
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• Diastereomers are stereoisomers whose molecules are not
mirror images of each other.
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4.2 Enantiomers and Chiral Molecules
• Enantiomers occur only with compounds whose molecules are chiral.
• A chiral molecule is one that is not identical with its mirror image.
• Objects (and molecules) that are superposable on their mirror
images are achiral.
The mirror image of a left hand is the right hand. Left and right hands are
not superposable.
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Example: 2-butanol
(a)3-D drawings of 2-butanol enantiomers I and II; (b) Models (c) An unsuccessful
attempt to superpose models I and II.
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• Stereocenter: an atom bearing groups of such nature that an
interchange of any two groups will produce a stereoisomer.
➢ A tetrahedral atom with four different groups attached to it is a
stereocenter (chiral center, stereogenic center). By convention,
atoms are designated with an asterisk (*).
2-butanol
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A demonstration of chirality of a
generalized molecule with
one chiral center.
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(a) 2-Propanal and its mirror image
(b) When either one is rotated, the two structures are superposable.
They represent two molecules of the same compound.
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4.3 The Biological Importance of Chirality
• Chirality is a phenomenon that pervades the universe.
➢ The human body is structurally chiral.
➢ Helical seashells are chiral, and most are spiral like a right-handed screw.
➢ Many plants show chirality in the way they wind around supporting structures.
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4.4 More About the Biological Importance of Chirality
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4.5 Tests for Chirality: Planes of Symmetry
1. Superposability of the models of a molecule and its mirage:
➢ If superposable, the molecule that they represent is achiral.
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(a) 2-chloropropane has a plane of symmetry and is achiral.
(b) Chlorobutane does not possess a plane of symmetry and is chiral.
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• The achiral hydroxy acetic acid molecule versus the chiral lactic
acid molecule:
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Review Problem:
Do the following molecules have a chirality center or not? If
there is, denote with asterisk.
1. 2-fluoropropane
2. 2-methylbutane
3. 2-chlorobutane
4. 2-methyl-1-butanol
5. 2-bromopentane
6. 3-methylpentane
7. 3-methylhexane
8. 1-chloro-2-methylbutane
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4.6 Nomenclature of Enantiomers: The (R-S) System
A. Designation of Stereocenter
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• (R) and (S) are from the Latin words rectus and sinister:
➢ In the case of isotopes, the isotope of greatest atomic mass has the highest
priority.
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2. Assign a priority at the first point of difference.
➢ When a priority cannot be assigned on the basis of the atomic number
of the atoms that are directly attached to the stereocenter, then the
next set of atoms in the unassigned groups are examined.
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3. View the molecule with the group of lowest priority pointing
away from you.
➢ If the direction from the highest priority(1) to the next highest(2)
to the next (3) is clockwise, the enantiomer is designated R.
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➢ If the direction is counterclockwise, the enantiomer is
designated S.
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4. The sign of optical rotation is not related to the R,S designation.
5. Groups containing double or triple bonds are assigned priority
as if both were duplicated or triplicated.
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Example: assignment of configuration to (+)-alanine
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Example: assignment of configuration to (-)-glyceraldehyde
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Review Problems
1. List the substituents in each of the following sets in order of priority,
from highest to lowest:
a) –Cl, -OH, -SH, -H
b) -CH3, -CH2Br, -CH2Cl, -CH2OH
c) -H, -OH, -CHO, - CH3
d) -CH(CH3)2, -C(CH3)3, -H, -CH=CH2
e) -H, -N(CH3)2, -O CH3, - CH3
2. Assign R or S designations to each of the following compounds:
H3 C Cl HO H
a) b)
H CH3
c)
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4.7 Fischer Projection Formulas
• Fischer Projection (Emil Fischer, 1891) Convention: the C chain
is drawn along the vertical line of the Fischer projection, usually
with the most highly oxidized end C atom at the top
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➢ Because a given chiral molecule can be drawn in many different ways, it’s
often necessary to compare two projections to see if they represent the
same or different enantiomers.
➢ To test for identity, FP can be moved around on the paper, but only two kinds
of motions are allowed.
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Allowed motions for Fischer Projection:
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➢ -H and –OH groups come out of the plane both before
and after a 180o rotation
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➢ Rotation of a Fischer Projection by 90o inverts its meaning:
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2. A Fischer projection can have one group held steady while the
other three rotate in either clockwise or counterclockwise
direction. The effect is simply to rotate around a single bond, which does
not change the stereochemistry.
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❖ Differentiate different Fischer projections:
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4.8 Properties of Enantiomers: Optical Activity
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• Enantiomers show different behavior only when they interact
with other chiral substances.
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• Enantiomers rotate the plane of plane-polarized light in equal
amounts but in opposite directions.
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• Plane-Polarized Light
➢ A beam of light consists of two mutually perpendicular oscillating fields:
an oscillating electric field and an oscillating magnetic field.
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➢ Oscillations of the electric field (and the
magnetic field) are occuring in all possible planes
perpendicular to the direction of propagation.
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• The Polarimeter: the device used for measuring the effect of
optically active compounds on plane-polarized light.
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The Measurement of Optical Rotation
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➢ If the tube contains an optically inactive substance, the observer will
detect the maximum amount of light passing through.
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• Specific Rotation
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• No correlation exists between the configuration of enantiomers
and the direction of optical rotation.
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4.9 Molecules with More than One Stereocenter
• Diastereomers: stereoisomers that are not mirror images of each
other
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• Meso Compounds:a special case of stereoisomers which occur
when a molecule has two chiral centers and each chiral center
has identical substituents
Stereochemical formulas for 2,3-dibromobutane
H Br Br H H H H H
Br H H Br Br Br Br Br
A B C D
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Stereochemical structures of tartaric acid
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