Isomers and stereochemistry

Isomers: Compounds that have the same molecular formula but do not have identical
structures. Two types: constitutional and stereoisomers
Constitutional isomers: Differ in the way atoms are connected.
Example: ethyl alcohol and dimethyl ether have the same molecular formula:
C2H6O. The oxygen in ethyl alcohol is bonded to a carbon and to a hydrogen,
whereas the oxygen in dimethyl ether is bonded to two carbons.

Stereoisomers: Differ in the way atoms are arranged in space and are connected the same
way. Two types: cis – trans isomers and isomers that contain asymmetric centers.

Cis – trans isomers

Cis – trans isomers: Result from restricted rotation, that can be caused either by a double
bond or a cyclic structure.
Cis isomer: Has the hydrogens on the same side of the double bond.
Trans isomer: Has the hydrogens on opposite sides of the double bond.
Example: Alkene 2- pentene can exist as cis and trans isomers. (Double bond)

Example: Restricted rotation of cyclic compounds resulting in cis and trans isomers.
(Cyclic compounds)
A chiral object has a nonsuperimposable mirror image
Chiral: An object with a right-handed and left-handed form is said to be chiral.
Achiral: Objects that are not chiral.
Chiral object: An object that has a nonsuperimposable mirror image. In other words, the
mirror image is not the same as an image of the object itself.
Examples:

An asymmetric center is the cause of chirality in a molecule

Molecules can be chiral too; the usual cause is an asymmetric center.
Asymmetric center: Is an atom bonded to four different groups.
Example: 4- octanol has an asymmetric center in a carbon because it is bonded to
four different groups (H, OH, CH2CH2CH3, and CH2CH2CH2CH3). Notice that
the atoms immediately bonded to the asymmetric center are not necessarily different
from one another (the propyl and butyl groups are different even though the point at
which they differ is several atoms away from the asymmetric center).
Isomers with one asymmetric center
Enantiomers: Molecules that are nonsuperimposable mirror images of each other. Each
member of a pair of enantiomers is chiral. (Notice chirality is a property of an entire object
or an entire molecule)
Example:

How to draw enantiomers

Perspective formula: shows two of the bonds to the asymmetric center in the plane of the
paper, one bond as a solid wedge protruding forward out of the paper, and the fourth bond
as a hatched wedge extending behind the paper. The solid wedge and the hatched wedge
must be adjacent to one another. When you draw the first enantiomer, the four groups
bonded to the asymmetric center can be place around in any order. You then draw the
second enantiomer by drawing the mirror image of the first.

Naming enantiomers by the R, S system

For any pair of enantiomers with one asymmetric center, one member will have the R
configuration and the other will have the S configuration. Let’s first look at how we can
determine the configuration of a compound if we have a three-dimensional model.
When you have access to the model and can visualize spatial relationships:
1. Rank the groups or atoms bonded to the asymmetric center in order of
priority. The atomic numbers of the atoms directly attached to the asymmetric
center determine the relative priorities. The higher the atomic number, the higher
the priority.
2. Orient the molecule so that the group or atom with the lowest priority is
directed away from you. Then draw an imaginary arrow from the group or
atom with the highest priority to the group or atom with the next highest
priority. If the arrow points clockwise, the asymmetric center has the R
configuration. If the arrow points counterclockwise, the asymmetric center has the S
configuration.
When you don’t have access to the model and have trouble visualizing spatial relationships:
1. Rank the groups or atoms that are bonded to the asymmetric center in order of
priority.
 2. If the group or atom with the lowest priority is bonded by a hatched wedge,
draw and arrow from the group or atom with the highest priority to the group or
atom with the second highest priority. If the arrow points clockwise, the compound
has the R configuration, and if it points counterclockwise, the compound has the S
configuration.
3. If the group with the lowest priority is NOT bonded by a hatched wedge,
interchange two groups. The proceed as in step 2: draw an arrow from the group or
atom with the highest priority to the group or atom with the second highest priority.
Because you have interchanged two groups, you are determining the configuration
of the enantiomer of the original molecule. So, if the arrow points clockwise the
enantiomer (with interchanged groups) has the R configuration, which means the
original molecule has the S configuration. On the other hand, if the arrow points
counterclockwise, the enantiomer (with interchanged groups) has the S
configuration, which means the original molecule has the R configuration.

Isomers with more than one asymmetric center

The more asymmetric centers a compound has, the more stereoisomers it can have. If we
know the number of asymmetric centers, we can calculate the maximum number of
stereoisomers for that compound. A compound can have a maximum of 2n stereoisomers,
where n equals the number of asymmetric centers.
Diastereomers: Are stereoisomers that are not enantiomers
Enantiomers have identical physical properties (except for the way they interact with
polarized light) and identical chemical properties, so they react at the same rate with an
achiral reagent. Diastereomers have different physical properties, meaning different m
elting points, different boiling points, different solubilities, different specific rotations, and
so on, and different chemical properties, so they react with an achiral reagent at different
rates.