Types of Isomers

Also, geometrical isomers

Constitutional isomers
are really different types
Stereoisomers are very
of molecules in terms of
similar in characteristics
characteristics and
and reactivity. Other
reactivity
molecules may interact
with stereoisomers in a
Shoe vs. Glove similar fashion but the
results may be quite
different.

Left Shoe vs. Right Shoe

Isomer is a very vague and over-used term. The specific terms

are much more useful for describing molecules.
 Stereoisomeric Definitions

Superimposable - spatially identical in 3D - baseball hats

Chiral - object whose mirror image is nonsuperimposable - shoes, gloves

Enantiomers - pair of chiral molecules that are mirror images of one another - enantiomer
is one molecule of the pair - pair of gloves

Diastereomers - pair of chiral molecules that have the same connectivity, but are not
superimposable and not mirror images. - a pair of hands in which one of the index fingers
curves backwards.

Asymmetric atom or stereocenter - in most of organic chemistry an atom with at least 4

different substituents. For carbon, four different substituents
 Ramifications of Stereochemistry

Chiral objects distinguish between other chiral objects

- right hand fits the right glove
Chiral molecules distinguish between enantiomeric molecules
- smell receptor site will produce a different “signal” or smell
for two enantiomers

Enantiomers are identical except in a chiral environment

-same melting point, boiling point, IR, polarity, solubility

Diastereomers are different molecules, any similarities are

coincidental.
Chirality

Hands are Chiral

Hammers are not Chiral

(Achiral)
 Chiral Molecules and Reaction
Br

Br2
+ HBr
light

Br Br

Bromination of butane produces two molecules that are:

-chiral
-stereoisomers
-enantiomers
 Absolute Configuration: R and S
R - rectus, Latin, right S - sinister, Latin, left

Absolute configurations are a method of nomenclature for stereogenic centers.

Steps to determine absolute configuration

1. Assign a ranking to each of the four different substituents
-ranking is determined by atomic number and then by multiplicity
-the lower rank is assigned a value of 4, while the highest rank is
assigned a value of 1.
2. Your right thumb is placed pointing down the lowest ranking bond.
3. If the curvature of your hand can pick-up the substituents in decreasing
order, e.g. 1-2-3, then the stereogenic center is R. If you cannot pick-up in 1-
2-3 order than the assignment is S
 Examples of R and S Determination
1 4
Br
H

* H 4
1
S Cl
3 3 S
2
S * Br
3 * 1
22
4H H
Br 1 4

*
R
2 3
Comparing the R and S configurations is an absolute
method of determining diastereomers from
enantiomers
Cl
Cl
enantiomers Mirror - enantiomers
R S
RS : SR
CH3 CH3
S R

Cl
diastereomers R Not Mirror - diastereomers
RS : RR
CH3
R
Polarization Change