Here's my condensed version of stereochemistry followed by some questions.

Stereoisomers are compounds that contain the same atoms bonded in the same sequence, but differ
in their 3-D arrangement. If they are mirror image pairs, they are enantiomers. If they are not, they are
diastereomers.

Br H H Br

stereoisomers diastereomers
Any material that rotates plane polarized light is optically active (also meaning it is chiral and not
superimposable with its mirror image). These mirror image pairs are called enantiomers. Earlier this
semester, we studied some stereoisomeric alkenes. For instance, trans-stilbene and cis-stilbene are
stereoisomers. What is the stereoisomeric relationship between these alkenes? They are diastereomers,
since they are not mirror images of each other. Neither the cis nor trans form of stilbene is chiral. Why?
Trans-stilbene and its mirror image are shown below (the dashed line is supposed to be a mirror). Notice
that they are the same compound and can be superimposed (same thing for the cis form). Thus, trans-
stilbene and cis-stilbene are not chiral nor are they opically active. The lack of a chiral carbon also tips us
off to this fact (although there are chiral compounds that lack a chiral atom.

Ph Ph

Ph Ph

The presence of a single chiral carbon in the compound (also called an asymmetric carbon) will
mean the compound is chiral. A chiral carbon is identified as a tetrahedral (sp3) carbon with 4 different
groups attached. If a compound has more than one chiral carbon, it may or may not be chiral (see the cis-
1,2-dimethylcyclohexane in the first figure. It has two chiral carbons yet is achiral).
The real test for chirality is this: draw a compound's mirror image; is it superimposable (meaning
is it the same thing you started with)? Remember, try to visualize the 3-D structures of the molecules, and
see if you can “pick it up” and superimpose it on top of the original. If you can superimpose the mirror
images, they are the same compounds, and they are not chiral nor optically active. If you cannot, they are
mirror-image isomers and are enantiomers. Another option is to look for a way to bisect the molecule into
equal halves. If you can cut it in half and the halves are mirror images (meaning it has a “plane of
symmetry”), it is not chiral. See example below, where the compound has two chiral carbons, yet has a
plane of symmetry and thus is achiral. It is superimposable with its mirror image.

CH3

Br H

C 2R, 3S-2,3-dibromobutane

"meso" form
C

Br H

CH3

The asymmetric carbons in chiral molecules are denoted (R) or (S) by rules we discussed in class.
Each enantiomer will rotate plane polarized light in the equal but opposite direction as its mirror image
counter part. A racemic (50/50 mixture) will not rotate the light at all. A pure compound that is chiral will
have a specific rotation ([) that is a property of that compound, much like a melting point or density. The
optical purity of a sample (also called enantiomeric excess) is the percentage of a given mixture’s specific
rotation divided by the pure enantiomer's specific rotation. Thus, a sample of 50% optical purity of an (S)
enantiomer means that 50% is pure (S), and the other 50% is racemic. Thus the sample consists of 75% (S)
and 25% (R). There is no relationship between the direction an enantiomer will rotate light (+ or -)
and its stereochemical configuration (R or S).
 Diastereomers are stereoisomers that are not enantiomers. Compounds that have more than one
chiral center (like 2,3-dibromobutane or 1,2-dimethylcyclohexane) typically will have diastereomeric forms
in addition to enantiomeric forms. While enantiomers have identical physical properties (mp, bp,
solubility), diastereomers do not. Meso compounds are compounds with chiral carbons, but are identical to
their mirror image. The meso form (C) and the enantiomers (A and B) of 2,3-dichlorobutane are shown
below. Note that the meso form is not optically active, since its mirror image is not a different compound.

CH3 CH3 CH3

H Cl Cl H H Cl

Cl H H Cl H Cl
CH3 CH3 CH3

(2S,3S)-2,3-dichlorobutane (2R,3R)-2,3-dichlorobutane meso-1,2-dichlorobutane

A B C

`Fischer projections are used in biology and biochemistry to depict stereoisomers using 2-D
structures. Most commonly, these are used for carbohydrates or amino acids, but they can be used for any
organic molecules. In Fischer projections, the vertical bonds go into the page, the horizontal bonds come
out. Once you realize what you are looking at, they are fairly straight-forward. For instance, (S)-1-bromo-1-
chloroethane is shown below in a 3-D form and a Fischer Projection.

H H

Cl Br
Br
H3C
Cl
CH3
Worksheet questions:
1) Assign (R) or (S) designations to each asymmetric carbon in the following compounds.

H3C H H Br CH2CH3

H F CH3
HO
CH2CH2 CH3

H CH3
CH2CH3
H Ph
Ph Ph
H Ph
H3C CH3
CH3

CH3
OH Br H
H Br H CH3 CH3
Cl H H CH3 H3 C
H H Br
CH3

2. Draw the 4 stereoisomers of 3-methyl-2-pentanol and give the relationship of each to the others.
3) Give the stereochemical relationship between the following pairs (same, enantiomers, diastereomers,
conformational isomers)
a) OH
CHO CHO
OH HO
H Ph Ph H
OH e)
H Ph Ph H
CHO CHO

H CH3
H H
b)
CH3 H
CH3 H2N NH2
CH3 CH2CH3 H3CH2C
f)
H H
H2N NH2

H3C H H H CH3 Ph H
Ph
c)
Br H
g)

Br H

CH3
Br
H Br H Br
d)
H CH3 Br H
CH3
CH3

Given the specific rotation of pure (+)-2-butanol is +13.50, answer questions 4-6. Note: there is no
correlation between +, - and R, S. So you would have no way of knowing which R,S enantiomer rotates
light in which direction unless you are told or find it experimentally in lab. In the case of 2-butanol, it
turns out the (S) enantiomer rotates light to the right, meaning it’s the (+) enantiomer.

4) Calculate the optical purity (or enantiomeric excess) and the observed rotation of a mixture containing 6
g (+)-2-butanol and 4 g (-)-2-butanol.

5) When (R)-2-bromobutane is heated in water, 2-butanol is formed. Propose a mechanism (we haven’t
seen this yet, so don’t worry if you can’t. Hint: the C-Br bond heterolytically breaks and you get a 20
carbocation as the intermediate). The reaction forms twice as much (S)-2-butanol as the (R) form.
Calculate the optical purity of the solution and the specific rotation of the product.
6) If a sample of 2-butanol is found to have a specific rotation of +0.50, what are the percentages of each
isomer?

7) Draw the meso form of 2,3-dichlorobutane as both a dashed-wedged structure and a Fischer projection.
Name a diastereomer of this compound.

8) Draw the chair form of cis-1,2-dibromocylcohexane. Draw its mirror image. Are these superimposable
(you should see that the answer is “no”). But why, then, did we learn in lecture that this molecule is
achiral, if it has a non-superimposable mirror image? (This would have been a good exam question.
Maybe I shouldn’t have used it here.)

9) (+)-Tartaric acid has a specific rotation of +120. Calculate the observed rotation of a mixture of 68%
(+) and 32% (-) tartaric acid.