Chapter 4: Chirality.

Levels of Organic Structures:

There are different levels to describe organic compounds:
 Composition: molecular formula (XxYyZz)
 Constitution: the way the atoms are connected, bonding pattern
 Configuration: 3-D position of atoms
 Conformation: position of groups with respect to bond rotation

Each of these levels are associated with a type of isomerism.

Types of Isomers:
Isomer: compounds that have the same molecular formula but different structural
formula.
Types:
 Constitutional: have different arrangements of atoms (CH3-CH2-O-CH2-CH3
vs. CH3-CH2-CH2-CH2-OH: both have MF C4H10O)
 Conformational: have different rotation about a single bond

 Configurational: have different atom arrangement, can either be called cis or

trans
Stereochemistry
Stereochemistry refers to chemistry in 3 dimensions.
Note: A consequence of a tetrahedral arrangement of bonds to carbon, is that 2
compounds may differ because the arrangement of their atoms in space is different.
Stereoisomers: Isomers that have the same constitution (MF and connectivity of
atoms) but differ in the spatial arrangement of their atoms.

Stereoisomers:
The mirror image of your right hand is your left hand; however, they are not
superimposable.
Chiral molecules: molecules that have a mirror image but are not superimposable
(Ex: the hand). Mostly occurs in molecules that contain a carbon attached to 4
different groups.
Achiral molecules: molecules that have a mirror image and can be superimposable
(Ex: pencil).
Note: any molecule that has a mirror plane or an inversion center cannot be chiral
because they can be superimposable.
Example of chiral molecule:

To make sure the molecule cannot be superimposed, turn it 180o.

Example:

Example of achiral molecule:

Enantiomers: a relation between a molecule and its nonsuperimposable mirror

image. A chiral molecule can only have 1 enantiomer.
Diastereomers: a relation between 2 molecules that are not mirror images of each
other. Mostly shown in configurational isomers.
The Chirality Center:
Molecules of the general type xyCwz are chiral when x, y, w, and z are different
substituents.

A tetrahedral carbon atom that is connected to 4 different substituents is called the

chiral center or a stereogenic center (stereocenter).
The presence of only one stereogenic center is an easy way to determine if the
molecule is chiral or not.

Note: carbons that have a double or triple bond cannot be stereogenic centers.
A carbon atom in a ring can be a stereogenic center if it is connected to 2 different
substituents and the path traced around the ring from that carbon in 1 direction
different from the one traced in the second direction.
Isotopes: Elements that have the same number of protons but different number of
neutrons.
Isotopes qualify as different substituents at a stereogenic center.
D: Deuterium = 2H

T: Tritium = 3H

Everything mentioned concerns molecules with only one stereogenic center.

Molecules with more than one stereogenic center could be chiral or achiral.
Symmetry in Achiral Structures
A molecule that has a plane of symmetry or a center of symmetry (inversion
center) is superimposable on its mirror image and is achiral.
Plane of symmetry: an internal reflection plane.

Inversion center: a point through which all atoms are projected.

A point is an inversion center if the line drawn from it to one element is extended
at an equal distance, will meet an identical element.

Any molecule with a plane or center of symmetry is achiral: however, their

absence doesn’t necessarily mean the molecule is chiral.
Optical Activity
Optical activity is the ability of a chiral substance to rotate the plane of plane-
polarized light and is measured using an instrument called a polarimeter.

The light used to measure optical activity has 2 properties:

1. A single wavelength.
2. Is plane polarized.
The wavelength used most often is 589 nm which is the yellow light produced by
the light.
A beam of unpolarized light is transformed to plane-polarized light by passing it
through a polarizing filter, which removes all the waves except those that have
their electric field vector in the same plane. This plane-polarized light now passes
through the sample tube. The sample is “optically active” if it rotates the plane of
polarized light. The direction and magnitude of rotation are measured using a
second polarizing filter (the “analyzer”) and cited as α, the observed rotation.
To be optically active, the sample must contain a chiral substance and one
enantiomer must be present in excess of the other.
A substance that does not rotate the plane of polarized light is said to be optically
inactive. All achiral substances are optically inactive.
Enantiomers have almost all identical physical properties
Enantiomeric forms of a chiral molecule cause a rotation of the plane of
polarization in exactly equal amounts but in opposite directions.
A solution containing equal quantities of enantiomers exhibits no net rotation. They
are called racemic mixtures and are optically inactive.
However, when one enantiomer is in excess, a net rotation of the plane is observed.
A substance is homochiral or enantiopure if all the molecules present are the same
enantiomer.
When we have a mixture of enantiomers where one isomer is present in larger
amounts, we use enantiomeric excess (ee) and enantiomeric ration (er) to describe
the mixture:
ee= (%major enantiomer) – (%minor enantiomer)
er= (%major enantiomer) : (%minor enantiomer)
Rotation of the plane of polarized light in the clockwise sense is taken as positive
(+) (dextrorotatory)
Rotation of the plane of polarized light in the counterclockwise sense is taken as
negative (-)(levorotatory)
Example: Enantiomers of 2 butanol are called (+)-2-butanol and (-)-2-butanol: the
racemic mixture is called (+)-2-butanol
The observed rotation α depends on how many molecules the light beam
encounters.
Ex: a polarimeter tube twice the length of another or a solution with twice the
concentration of another produced twice the observed rotation.
To account for the path length and concentration, chemists use the term specific
rotation and is calculated form the observed rotation using:
100 ∝
[ ∝ ]=
c∗l

c is the concentration of the sample in grams/100ml solution

l is the length of the polarimeter tube in decimeter (1 dm= 10cm)
If c is in g/ml use:
 ∝
[ ∝ ]=
c∗l

The specific rotation is a physical property.

Optically purity: enantiomeric excess and is calculated using specific rotation:
specific rotationof sample
ee=Optical purity= x 100
specific rotationof pure enantiomer
moles of one enantiomer−moles of another enantiomer
% enantiomeric excess= x 100
total moles of both enantiomer