Chapter-4 Stereochemistry

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CHM 033

GENERAL ORGANIC CHEMISTRY

IV. Stereochemistry

Reference: Organic Chemistry. Solomons and Fryhle. 8th Edition

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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.

• Enantiomers are steroisomers whose molecules are nonsuper-


posable mirror images of each other.

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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

I and II are mirror images of each


Other but not superposable:
enantiomers

(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.

III and IV are not superposable,


Hence, enantiomers.

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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.

❖ 2-Propanol does not have a stereocenter.

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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.

❖ The honeysuckle winds as left-handed helix.

❖ The bind-weed winds as a right-handed way.

• Most of the molecules that make up plants and animals are


chiral and usually only one form of the chiral molecule occurs
in a given species.

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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.

➢ If nonsuperposable, the molecules that they represent are chiral.

2. The presence of a single tetrahedral stereocenter: chiral molecule.

3. The presence of a plane of symmetry: achiral molecule.


➢ A plane of symmetry (also called a mirror plane) is an imaginary plane that
bisects a molecule in such a way that the two halves of the molecule are
mirror images of each other.
➢ The plane may pass through atoms, between atoms or both.

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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:

➢ Hydroxyacetic acid has a plane of symmetry.


➢ Lactic acid has none.

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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

2-Butanol (sec-Butyl alcohol)

• RS Cahn (England), CK Ingold (England) and V Prelog (Switzerland)


devised the (R-S) system (Sequence Rule) for designating the
configuration of chiral C atoms.

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• (R) and (S) are from the Latin words rectus and sinister:

➢ R configuration: clockwise (rectus, “right”)


➢ S configuration: counterclockwise (sinister, “left”)

B. The (R-S) System: Cahn-Ingold-Prelog System


1. Each of the four groups attached to the stereocenter is assigned
a priority.
➢ Priority is first assigned on the basis of the atomic number of the atom that
is directly attached to the stereocenter.
➢ The group with the lowest atomic number is given the lowest priority, 4; the
group with the next higher atomic number is given the next priority, 3
and so on.

➢ 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

Vertical lines : bonds going into the page


Horizontal lines: bonds coming out of the page

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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:

1. 180o rotation (not 90o or 270o):

➢ -COOH and –CH3 go into plane of paper in both projections

➢ -H and –OH come out of plane of paper in both projections

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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:

❖ -COOH and –CH3 go into plane of paper in one projection


but come out of plane in the other projection

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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

• Enantiomers have identical physical properties such as B.pts.,


M. pts.,refractive indeces and solubilities in common solvents
except optical rotation.

➢ Many of these properties are dependent on the magnitude of the


IMFA operating between the molecules. For molecules that are
mirror images of each other, these forces will be identical.

➢ have identical IR, UV and NMR spectra if they are measured in


achiral solvents

➢ have identical reaction rates with achiral reagents

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• Enantiomers show different behavior only when they interact
with other chiral substances.

➢ show different rates of reaction toward other chiral molecules


➢ show different solubilities in chiral solvents that consist of a
single enantiomer or an excess of a single enantiomer.

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• Enantiomers rotate the plane of plane-polarized light in equal
amounts but in opposite directions.

➢ Separate enantiomers are said to be optically active compounds.

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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.

❖ The waves depicted here occur in all possible in ordinary light.

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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.

➢ When ordinary light is passed through a polarizer,


the polarizer interacts with the electric field so
that the electric field of the light emerges from
the polarizer (and the magnetic field
perpendicular to it) is oscillating only in one
plane: plane-polarized light.

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• The Polarimeter: the device used for measuring the effect of
optically active compounds on plane-polarized light.

The principal working parts of a


Polarimeter

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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.

➢ If the tube contains an optically active substance, the plane of


polarization of light will be rotated as it passes through the tube.

➢ If the analyzer is rotated in a clockwise direction, the rotation a


(measured in degree) is said to be positive (+), and if
counterclockwise, a is negative (-).

➢ A substance that rotates the plane-polarized light in the clockwise


direction is said to be dextrorotatory, and the one that rotates the
plane-polarized light in a counterclockwise direction is said to be
levorotatory (Latin dexter, right; laevus, left.)

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• Specific Rotation

➢ depends on the temperature and wavelength of light employed

➢ its magnitude is dependent on solvent when solutions are measured.

• The direction of rotation of plane-polarized light is often


incorporated into the names of optically active compounds.

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• No correlation exists between the configuration of enantiomers
and the direction of optical rotation.

• No correlation exists between the (R) and (S) designation 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

➢ Enantiomers must have opposite (mirror-image) configurations at all


sterogenic centers.
➢ Diastereomers must have opposite configurations at some (one or more)
stereogenic centers, but the same configurations at other stereogenic
centers.
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The four diastereomers of threonine (2-amino-3-hydroxybutanoic acid)

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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

➢ A and B are nonsuperposable; enantiomers.


➢ C and D are superposable; two orientations
of same molecule: meso compounds.

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Stereochemical structures of tartaric acid

➢ Meso compounds, because they are achiral, are optically inactive.

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