Chapter 5

Stereoisomerism
Review of Concepts
Fill in the blanks below. To verify that your answers are correct, look in your textbook at the end of
Chapter 5. Each of the sentences below appears verbatim in the section entitled Review of Concepts and
Vocabulary.
• ______isomers have the same connectivity of atoms but differ in their spatial arrangement.
• Chiral objects are not superimposable on their ____________________. The most common
source of molecular chirality is the presence of a _______________, a carbon atom bearing
______ different groups.
• A compound with one chirality center will have one non-superimposable mirror image, called its
_______________.
• The Cahn-Ingold-Prelog system is used to assign the ______________ of a chirality center.
• A polarimeter is a device used to measure the ability of chiral organic compounds to rotate the
plane of ____________________ light. Such compounds are said to be ____________ active.
• A solution containing equal amounts of both enantiomers is called a __________ mixture. A
solution containing a pair of enantiomers in unequal amounts is described in terms of
enantiomeric _________ (ee).
• For a compound with multiple chirality centers, a family of stereoisomers exists. Each
stereoisomer will have at most one enantiomer, with the remaining members of the family being
______________.
• A ______ compound contains multiple chirality centers but is nevertheless achiral because it
possesses reflectional symmetry.
• __________ projections are drawings that convey the configuration of chirality centers, without
the use of wedges and dashes.

Review of Skills
Fill in the blanks and empty boxes below. To verify that your answers are correct, look in your textbook at
the end of Chapter 5. The answers appear in the section entitled SkillBuilder Review.

SkillBuilder 5.1 Identifying cis-trans Stereoisomerism

SkillBuilder 5.2 Locating Chirality Centers

SkillBuilder 5.3 Drawing an Enantiomer

 CHAPTER 5 131

SkillBuilder 5.4 Assigning Configuration

SkillBuilder 5.5 Calculating specific rotation

SkillBuilder 5.6 Calculating % ee

SkillBuilder 5.7 Determining Stereoisomeric Relationship

SkillBuilder 5.8 Identifying Meso Compounds

SkillBuilder 5.9 Assigning configuration from a Fischer projection

132 CHAPTER 5

Common Mistakes to Avoid

When drawing a chirality center, the four groups connected to the chirality center must be drawn so that
one group is on a wedge (which indicates that it is coming out of the page), and one group is on a dash
(which indicates that it is going behind the page), and two groups are on straight lines (which indicate that
these two groups are in the plane of the page), as seen in each of the following drawings:

Notice that in all of these cases, the two straight lines form a V, and neither the dash nor the wedge is
placed inside that V. This is very important. If either the dash or the wedge is placed inside the V, the
drawing becomes ambiguous and inaccurate. Don’t make this mistake, as it is a common mistake:

The drawings above do not make any sense, and if a chirality center is drawn like either of the drawings
above, it would be impossible to assign a configuration to the chirality center. Never draw a chirality
center that way. For the same reason, never draw a chirality center like this:

These two drawings imply square planar geometry, which is not the case for an sp3 hybridized carbon atom
(the geometry is tetrahedral). In some rare cases, you might find a chirality center for which three of the
lines are drawn as straight lines, as in the following example:

This compound has one chirality center, and its configuration is unambiguous (and therefore acceptable),
although you will not encounter this convention often. In most cases that you will encounter in this course,
a chirality center will be drawn as two lines (making a V), and one wedge and one dash that are both
outside of the V:
 CHAPTER 5 133

Solutions
5.1.
(a) The methyl groups are on opposite sides of the (g) The carboxylic acid groups (highlighted below) are
double bond, so this compound has a trans configuration. on the same side of the double bond, so this compound
has a cis configuration.

(b) Two identical groups (fluorine atoms) are connected

to the same position. Therefore, this compound is not
stereoisomeric.

5.2. We first draw a bond-line structure, which makes it

easier to see the groups that are connected to each of the
double bonds.
(c) The hydrogen atoms are on opposite sides of the
double bond, so this compound has a trans configuration.
Each of the double bonds has two identical groups
(hydrogen atoms) connected to the same position.

(d) The hydrogen atoms are on opposite sides of the

double bond, so this compound has a trans configuration.
As such, neither double bond exhibits stereoisomerism,
so this compound does not have any stereoisomers.

5.3.
(a) Compound X must contain a carbon-carbon double
bond in the trans configuration, which accounts for four
of the five carbon atoms:

(e) The phenyl groups (highlighted below) are on

opposite sides of the double bond, so this compound has
a trans configuration.
Now we must decide where to place the fifth carbon
atom. We cannot attach this carbon atom to a vinylic
position (C2 or C3), as that would give a double bond
that is not stereoisomeric, and compound X is supposed
to have the trans configuration.

(f) There are three butyl groups in this case, and two of
them (highlighted below) are connected to the same
position. Therefore, this compound is not
stereoisomeric. Therefore, we must attach the fifth carbon atom to an
allylic position, giving the following compound:

(b) Compound Y possesses a carbon-carbon double bond

that is not stereoisomeric, which means that it must
contain two identical groups connected to the same
134 CHAPTER 5

vinylic position. Those identical groups can be methyl 5.5. Recall that constitutional isomers are compounds
groups, as in the following compound, that share the same molecular formula, but differ in
constitution (the connectivity of atoms). There are two
different ways that four carbon atoms can be connected
together. They can be connected in a linear fashion
(below left), or they can be connected with a branch
(below right).

or the identical groups can be hydrogen atoms, as in the

following three compounds:

For each of these skeletons, we must consider the

different locations where a bromine atom can be placed.
In the linear skeleton, the bromine atom can either be
placed at C1 or at C2.

5.4. In each of the following cases, we ignore all sp2 Placing the bromine atom at C3 is the same as placing it
hybridized carbon atoms, all sp hybridized carbon atoms, at C2:
and all CH2 and CH3 groups. We identify those carbon
atoms (highlighted below) bearing four different groups:
(a) This compound has two chirality centers:

Similarly, placing the bromine atom at C4 is the same as

placing it at C1.
Now let’s consider the branched skeleton. There are two
unique locations where the bromine atom can be placed
(either at C1 or at C2).
(b) This compound has five chirality centers:

Placing the bromine atom at C3 or C4 is the same as

placing it at C1:

(c) This compound has five chirality centers:

In summary, we have found four constitutional isomers

with molecular formula C4H9Br, shown below. Only one
of these isomers exhibits a carbon atom that is connected
to four different groups, which makes it a chirality
center.

(d) This compound has only one chirality center:

5.6. The first compound has three chirality centers:

 CHAPTER 5 135

(b) To draw the enantiomer, we simply redraw the

structure in the problem statement, except that we
replace the wedge with a dash, as shown:

This is apparent if we assign the configuration at C1 and

C3 of the cyclohexane ring. In the first compound, the
configuration at C1 is different than the configuration at (c) To draw the enantiomer, we simply redraw the
C3. As a result, there are four different groups attached structure in the problem statement, except that we
to the C2 position. That is, C1 and C3 represent two replace the wedge with a dash, and we replace the dash
different groups: one with the R configuration and the with a wedge, as shown:
other with the S configuration. In contrast, consider the
configuration at C1 and C3 in the second compound.
Both of these positions have the same configuration, and
therefore, the C2 position in that compound does not
have four different groups. Two of the groups are
identical, so C2 is not a chirality center.
There is an alternative argument that can be provided to
explain why C2 is not a chirality center in the second
compound. To understand this alternative argument, (d) To draw the enantiomer, we simply redraw the
let’s treat the C2 position “as if” it is a chirality center structure in the problem statement, except that we
and let’s draw both possible configurations for that replace the wedge with a dash, as shown:
location:

If we compare these two structures, we find that rotating

(e) To draw the enantiomer, we simply redraw the
the first structure 180 degrees about a vertical axis
structure in the problem statement, except that we
generates the second structure. As such, these two
replace the wedge with a dash, and we replace the dash
structures represent the same compound. Therefore, C2
with a wedge, as shown:
cannot possibly be a chirality center, because it does
NOT have two different configurations. In contrast, the
C2 position in the first compound DOES have two
different configurations. The following two compounds
are indeed different, which proves that C2 is a chirality
center in the first compound.

(f) To draw the enantiomer, we simply redraw the

structure in the problem statement, except that we
replace the wedge with a dash, and we replace the dash
with a wedge, as shown:

5.7.
(a) To draw the enantiomer, we simply redraw the
structure in the problem statement, except that we
replace the wedge with a dash, as shown:

(g) Wedges and dashes are not drawn in the structure in

the problem statement, because the three-dimensional
geometry is implied by the drawing. In this case, it will
be easier to place the mirror on the side of the molecule,
giving the following structure for its enantiomer:
136 CHAPTER 5

5.8. In this case, it will be easiest to place the mirror

behind the molecule, giving the following structure for
its enantiomer:

5.9. (c) This compound has two chirality centers, shown

(a) This compound has two chirality centers, shown below. The following prioritization schemes led to the
below. The following prioritization schemes led to the assignment of configuration for each chirality center.
assignment of configuration for each chirality center.

(b) This compound has two chirality centers, shown (d) This compound has three chirality centers. The
below. The following prioritization schemes led to the following prioritization schemes led to the assignment of
assignment of configuration for each chirality center. configuration for each chirality center.
 CHAPTER 5 137

5.10.
(a) This compound is (S)-limonene, as determined by the
following prioritization scheme:

(b) This compound is (R)-limonene, as determined by

the following prioritization scheme:
(e) This compound has four chirality centers, shown
below. The following prioritization schemes led to the
assignment of configuration for each chirality center.

(c) This compound is (S)-limonene, as determined by the

following prioritization scheme:

(d) This compound is (R)-limonene, as determined by

the following prioritization scheme:

α
5.11. specific rotation = [α] =
cl
( 1.47º )
= = +25.6
(0.0575 g/mL)  (1.00 dm)
(f) This compound has two chirality centers, shown
below. The following prioritization schemes led to the
assignment of configuration for each chirality center.
138 CHAPTER 5

α
5.12. specific rotation = [α] =
cl
( 2.99º )
= = -31.5
(0.095 g/mL)  (1.00 dm)

α
5.13. specific rotation = [α] =
cl
( 0.57 º ) 5.19.
= = +2.2 (a) We assign a configuration to each chirality center in
(0.260 g/mL)  (1.00 dm)
each compound, and we compare:

5.14.
α
[α] =
cl
In the first compound, both chirality centers have the R
α = [α]  c l configuration, while in the second compound, both
chirality centers have the S configuration. These
compounds are mirror images of each other, but they are
= (-13.5)(0.100 g/mL)(1.00 dm) = -1.35 º nonsuperimposable. That is, if you try to rotate the first
compound 180 degrees about a horizontal axis, you will
5.15. not generate the second compound (if you have trouble
seeing this, you may find it helpful to build a molecular
model). These compounds are therefore enantiomers.
(b) We assign a configuration to each chirality center in
each compound, and we compare:

5.16. In the first compound, the configurations of the chirality

centers are R and S, while in the second compound, they
are S and S. These compounds are stereoisomers, but
they are not mirror images of each other. Therefore, they
are diastereomers.

(c) We assign a configuration to each chirality center in

each compound, and we compare:

5.17.

In the first compound, the configurations of the chirality

centers are R and R, while in the second compound, they
are R and S. These compounds are stereoisomers, but
they are not mirror images of each other. Therefore, they
are diastereomers.

(d) We assign a configuration to each chirality center in

α each compound, and we compare:
5.18. Observed [α] =
cl
( 0.78º )
= = +2.2
(0.350 g/mL)  (1.00 dm)
 CHAPTER 5 139

(c) (d)

In the first compound, the configurations of the chirality

centers are R, S, and R, respectively. In the second
compound, they are S, S, and R. These compounds are
stereoisomers, but they are not mirror images of each
other. Therefore, they are diastereomers. (e) (f)

(e) We assign a configuration to each chirality center in

each compound, and we compare:

5.24.
(a) With two chirality centers, we would expect four
In the first compound, the configurations of the chirality
stereoisomers. However, there are only three
centers are R and S, while in the second compound, they
stereoisomers in this case, because the first one shown
are R and R. These compounds are stereoisomers, but
below is a meso compound.
they are not mirror images of each other. Therefore, they
are diastereomers.

5.20. There are three chirality centers, and only one of

these chirality centers has a different configuration in
these two compounds. The other two chirality centers
have the same configuration in both compounds. (b) With two chirality centers, we would expect four
Therefore, these compounds are diastereomers. stereoisomers. However, there are only three
stereoisomers in this case, because the first one shown
below is a meso compound.

5.21. (c) With two chirality centers, we would expect four

(a) Yes, there is a plane of symmetry that chops the stereoisomers. However, there are only three
goggles in half, with the right side reflecting the left side. stereoisomers in this case, because the first one shown
(b) Yes, there is a plane of symmetry that goes through below is a meso compound.
the handle of the cup.
(c) No, there is no plane of symmetry.
(d) Yes, there is a plane of symmetry that chops the
whistle in half.
(e) Yes, there are three planes of symmetry in this cinder
block.
(f) No, there are no planes of symmetry in a hand.

5.22. The cinder block (5.23e) has three planes of

symmetry, each of which chops the block in half.

5.23. Each of the following compounds has a plane of

symmetry, as shown:
(a) (b)

(d) With two chirality centers, there are four

stereoisomers (no meso compounds).
140 CHAPTER 5

(d) This chirality center has the S configuration, as

shown below:

5.27. It is helpful to use a numbering system when

converting one type of drawing into another. When
drawing each substituent in the Fischer projection, you
(e) With two chirality centers, we would expect four must decide whether it is on the right or left side of the
stereoisomers. However, there are only three Fischer projection. For each chirality center, make sure
stereoisomers in this case, because the first one shown that the configuration is the same as the configuration in
below is a meso compound. the bond-line drawing. If necessary, assign the
configuration of each chirality center in both the Fischer
projection and the bond-line drawing to ensure that you
drew the configuration correctly. With enough practice,
you may begin to notice some trends (rules of thumb)
that will allow you to draw the configurations more
quickly.
(a)

5.25. Each of these compounds is a meso compound and

does not have an enantiomer.

(b)

5.26.
(a) This chirality center has the R configuration, as
shown below:

(c)

(b) This chirality center has the S configuration, as

shown below:

5.28. <AQ> Question is from 3rd Ed.

<AQ>

(c) This chirality center has the S configuration, as 5.29. This compound has two chirality centers, shown
shown below: below. The following prioritization schemes led to the
assignment of configuration for each chirality center.
 CHAPTER 5 141

5.32 (a) The phosphorus atom has four different groups

attached to it (a methyl group, an ethyl group, a phenyl
group, and a lone pair). This phosphorous atom
therefore represents a chirality center. This compound is
not superimposable on its mirror image (this can be seen
more clearly by building and comparing molecular
5.30. To draw the enantiomer, we simply redraw the models).
structure in the problem statement, except that we (b) The chirality center has the S configuration,
replace the wedges with dashes, and we replace the determined by the prioritization scheme shown here.
dashes with wedges, as shown:

5.33. To assign the configuration, we must first assign

a prioritization scheme to the four atoms connected to
the chirality center:

5.31.
(a) In order to draw the enantiomer of paclitaxel, we
convert every wedge into a dash, and we convert every
dash into a wedge, as shown:
One of these atoms is H, so that atom is immediately
assigned the fourth priority. The remaining three atoms
are all carbon atoms, so for each of them, we prepare a
list of the atoms attached to them. Let’s begin with the
double bond. Recall that a double bond is comprised of
one  bond and one  bond. For purposes of assigning
configurations, we treat the  bond as if it were a  bond
to another carbon atom, like this:

We treat a triple bond similarly. Recall that triple bonds

are comprised of one  bond and two  bonds. As such,
each of the two  bonds is treated as if it were a  bond
(b) Paclitaxel has eleven chirality centers (highlighted to another carbon atom:
below).

This gives the following competition:

142 CHAPTER 5

Among these groups, the double bond is assigned the 5.34 (a) If we rotate the first structure 180 degrees about
third priority in our prioritization scheme, and we must a horizontal axis, the second structure is generated. As
continue to assign the first and second priorities. such, these two structures represent the same compound.
(b) These compounds have the same molecular formula,
but they differ in their constitution. The bromine atom is
connected to C3 in the first compound, and to C2 in the
second compound. Therefore, these compounds are
constitutional isomers.
(c) These compounds are stereoisomers, but they are not
mirror images of each other. Therefore, they are
We move one carbon atom away from the chirality diastereomers.
center, and we compare the following two positions: (d) If we assign a name to each structure, we find that
both have the same name: (S)-3-methylhexane.
Therefore, these structures represent the same
compound.
(e) These compounds are nonsuperimposable mirror
images of each other. Therefore, they are enantiomers.
(f) These structures represent the same compound
(rotating the first compound 180 degrees about a vertical
In each case, we must construct a list of the three atoms axis generates the second compound).
that are connected to each position. This is easy to do (g) These structures represent the same compound,
for the left side, which is connected to two carbon atoms which does not contain a chirality center, because there
and one hydrogen atom: are two ethyl groups connected to the central carbon
atom.
(h) These structures represent the same compound
(rotating the first compound 180 degrees about a vertical
axis generates the second compound).
(i) These compounds are nonsuperimposable mirror
images of each other. Therefore, they are enantiomers.
For the right side, the highlighted carbon atom is part of (j) These compounds have the same molecular formula
a triple bond, so we treat each  bond as if it were a (C6H12), but they differ in their constitution. Therefore,
sigma bond to another carbon atom: these compounds are constitutional isomers.
5.35.
(a) There are three chirality centers (n=3), so we expect
2n = 23 = 8 stereoisomers.
(b) There are two chirality centers (n=2), so we initially
expect 2n = 22 = 4 stereoisomers. However, one of the
stereoisomers is a meso compound, so there will only be
As such, the right side wins the tie-breaker:
3 stereoisomers.
(c) There are four chirality centers (n=4), so we expect 2 n
= 24 = 16 stereoisomers.
(d) There are two chirality centers (n=2), so we initially
expect 2n = 22 = 4 stereoisomers. However, one of the
stereoisomers is a meso compound, so there will only be
3 stereoisomers.
(e) There are two chirality centers (n=2), so we initially
expect 2n = 22 = 4 stereoisomers. However, one of the
stereoisomers is a meso compound, so there will only be
3 stereoisomers.
Our prioritization scheme indicates that the chirality
(f) There are five chirality centers (n=5), so we expect 2n
center has the R configuration:
= 25 = 32 stereoisomers.
5.36. In each case, we draw the enantiomer by replacing
all wedges with dashes, and all dashes with wedges. For
 CHAPTER 5 143

Fischer projections, we simply change the configuration

at every chirality center by switching the groups on the
left with the groups on the right:

(a) (b)

(b) In this case, there are two identical groups

(highlighted below) connected to the same vinylic
position. Therefore, this compound is not
stereoisomeric.
(c)

(d) (e)

(c) In this case, there are two methyl groups (highlighted

below) connected to the same vinylic position.
Therefore, this compound is not stereoisomeric.

(f)

5.37. The configuration of each chirality center is shown

below:
(a) (b)

(g)

(c)

(h)

(d) (e)

(f)

5.35.
(a) The hydrogen atoms are on opposite sides of the
double bond, so this compound has a trans configuration.
144 CHAPTER 5

(g) stereoisomers, but they are not mirror images of each

other. They are diastereomers.
(b) Each of the chirality centers has a different
configuration when comparing these compounds. As
such, these compounds are nonsuperimposable mirror
images. They are enantiomers.
(h) (i) (c) These structures represent the same compound
(rotating the first compound 180 degrees about a
horizontal axis generates the second compound).
(d) These compounds are nonsuperimposable mirror
images. Therefore, they are enantiomers.

5.43.
5.38. In this case, there is a 96% excess of A. The (a) One of the chirality centers has a different
remainder of the solution is a racemic mixture of both configuration in each compound, while the other
enantiomers (2% A and 2% B). Therefore, the chirality center has the same configuration in each
enantiomeric excess (ee) is 96%. compound. As such, these compounds are
stereoisomers, but they are not mirror images of each
5.39. This compound does not have a chirality center, other. They are diastereomers.
because two of the groups are identical: (b) Each of the chirality centers has a different
configuration when comparing these compounds. As
such, these compounds are nonsuperimposable mirror
images. They are enantiomers.
(c) Each of the chirality centers has a different
configuration when comparing these compounds. As
such, these compounds are nonsuperimposable mirror
Accordingly, the compound is achiral and is not optically images. They are enantiomers.
active. We thus predict a specific rotation of zero. (d) One of the chirality centers has a different
configuration in each compound, while the other
chirality center has the same configuration in each
5.40. compound. As such, these compounds are
α stereoisomers, but they are not mirror images of each
[α] = other. They are diastereomers.
cl
5.44.
α = [α]  c l (a) True.
(b) False. A meso compound cannot have an
= (-13.5)(0.100 g/mL)(1.00 dm) = -1.35 º enantiomer. Its mirror image IS superimposable.
(c) True. In a Fischer projection, all horizontal lines
5.41. We first draw a bond-line structure, which makes it represent wedges, and all vertical lines represent dashes.
easier to see the groups that are connected to each of the If we rotate the structure by 90 degrees, we are changing
double bonds. all wedges into dashes and all dashes into wedges.
Therefore, the new structure will be an enantiomer of the
original structure. Be careful though – you can only
rotate a Fischer projection by 90 degrees (to draw the
enantiomer) if there is one chirality center. If there is
Each of the double bonds has two identical groups
more than one chirality center, then you cannot rotate the
(hydrogen atoms) connected to the same position.
Fischer projection by 90 degrees in order to draw its
enantiomer. Instead, you must change the configuration
at every chirality center by switching the groups on the
left with the groups on the right.

5.45.
As such, neither double bond exhibits stereoisomerism, (a) This chirality center has the R configuration, as
so this compound does not have any stereoisomers. shown below:

5.42.
(a) One of the chirality centers has a different
configuration in each compound, while the other
chirality center has the same configuration in each
compound. As such, these compounds are
 CHAPTER 5 145

(b) This chirality center has the S configuration, as α

shown below: 5.47. specific rotation = [α] =
cl
( 0.47 º )
= = 63
(0.0075 g / mL)  (1.00 dm)

5.48.
(a) We must first rotate 180 degrees about the central
(c) This chirality center has the S configuration, as carbon-carbon bond, in order to see more clearly that the
shown below: compound possesses a plane of symmetry, shown below:

(d) This chirality center has the S configuration, as (b) We must first rotate 180 degrees about the central
shown below: carbon-carbon bond, in order to see more clearly that the
compound possesses a plane of symmetry, shown below:

5.46. For each chirality center, we follow the same

procedure that we used in the previous problem. We
(c) We must first convert the Newman projection into a
first redraw the chirality center so that there are two
bond-line drawing:
lines, one wedge and one dash:

Then, we assign priorities, and determine the

configuration. This process gives the following
configurations:
(a) (b)
Then, we rotate 180 degrees about the central carbon-
carbon bond, in order to see more clearly that the
compound possesses a plane of symmetry, shown below:

(c)

(d) This compound has a plane of symmetry as shown:

146 CHAPTER 5

5.49. As seen in Section 4.9, cyclobutane adopts a

slightly puckered conformation. It has two planes of
symmetry, shown below:

When drawn in this way, we can see clearly that one of

the chirality centers has a different configuration in each
compound, while the other chirality center has the same
configuration in each compound. As such, these
compounds are stereoisomers, but they are not mirror
images of each other. They are diastereomers.
(e) It might appear as if each of the chirality centers has a
different configuration when comparing these
compounds. However, each of these compounds has an
internal plane of symmetry (horizontal plane). As such,
both structures represent the same meso compound.
These two structures are the same.
(f) Each of the chirality centers has a different
configuration when comparing these compounds. As
such, these compounds are nonsuperimposable mirror
images. They are enantiomers.
(g) Each of the chirality centers has a different
configuration when comparing these compounds. As
such, these compounds are nonsuperimposable mirror
5.50. images. They are enantiomers. Be careful – rotating one
(a) One of the chirality centers has a different of these structures by 180 degrees does NOT generate
configuration in each compound, while the other the other structure. You may find it helpful to build a
chirality center has the same configuration in each molecular model to prove this to yourself.
compound. As such, these compounds are (h) If we rotate the first structure 180 degrees about a
stereoisomers, but they are not mirror images of each vertical axis, the second structure is generated. As such,
other. They are diastereomers. these two structures represent the same compound
(b) These compounds have the same molecular formula (which is meso).
(C8H16), but they differ in their constitution. The first
compound is 1,2-disubstituted, while the second 5.51.
compound is 1,3-disubstituted. Therefore, they are (a) The specific rotation of (R)-carvone should be the
constitutional isomers. same magnitude but opposite sign as the specific rotation
(c) Let’s redraw the compounds in a way that shows the of (S)-carvone (assuming both are measured at the same
configuration of each chirality center without showing temperature). Therefore, we expect the specific rotation
the conformation (chair). This will make it easier for us of (R)-carvone at 20 °C to be –61.
to determine the stereoisomeric relationship between the
two compounds: (b)

When drawn in this way, we can see clearly that one of

the chirality centers has a different configuration in each
compound, while the other chirality center has the same
configuration in each compound. As such, these (c) Since the ee is 90%, the mixture must be comprised
compounds are stereoisomers, but they are not mirror of 95% (R)-carvone and 5% (S)-carvone (95 – 5 = 90).
images of each other. They are diastereomers.
(d) Let’s redraw the compounds in a way that shows the 5.52.
configuration of each chirality center without showing (a) This compound has a non-superimposable mirror
the conformation (chair). This will make it easier for us image, and therefore it is chiral.
to determine the stereoisomeric relationship between the (b) This compound has a non-superimposable mirror
two compounds: image, and therefore it is chiral.
(c) This compound lacks a chirality center and is
therefore achiral.
 CHAPTER 5 147

(d) This compound has a non-superimposable mirror (b) We first convert the Newman projection into a bond-
image, and therefore it is chiral. line drawing:
(e) This compound is a meso compound, which we can
see more clearly if we rotate the central carbon-carbon
bond by 180 degrees, shown below. Since the
compound is meso, it must be achiral.

When drawn in bond-line format, we can see that the

(f) This compound has an internal plane of symmetry compound has two chirality centers (highlighted):
and is therefore a meso compound. As such, it must be
achiral.
(g) This compound has an internal plane of symmetry
(chopping the OH group in half and chopping the methyl
group in half) and is therefore a meso compound. As
such, it must be achiral. This compound is chiral and therefore optically active.
(h) This compound has a non-superimposable mirror
image, and therefore it is chiral. (c) This compound has a non-superimposable mirror
(i) This compound has a non-superimposable mirror image, so it is chiral. Therefore, it is optically active.
image, and therefore it is chiral.
(j) This compound lacks a chirality center and is (d) Let’s redraw the compound in a way that shows the
therefore achiral. configuration of each chirality center without showing
(k) This compound has an internal plane of symmetry the conformation (chair). This will make it easier for us
and is therefore a meso compound. As such, it must be to evaluate:
achiral.
(l) This compound has an internal plane of symmetry
(shown below), and is therefore a meso compound. As
such, it must be achiral.

This compound has an internal plane of symmetry, so it

is a meso compound. As such, it is achiral and optically
inactive.

(e) This compound has a non-superimposable mirror

image, so it is chiral. Therefore, it is optically active.

(f) We first convert the Newman projection into a bond-

line drawing:
5.53.
(a) If we rotate the central carbon-carbon bond of the
Newman projection 180°, we arrive at a conformation in
which the two OH groups are eclipsing each other, the
two methyl groups are eclipsing each other, and the two
H’s are eclipsing each other.

This compound is 3-methylpentane, which does not have

a chirality center. Therefore, it is optically inactive.

In this eclipsed conformation, we can clearly see that the

molecule has an internal plane of symmetry (it is a meso
compound). Therefore, the compound is optically
inactive.
148 CHAPTER 5

(g) This compound has an internal plane of symmetry (a (c)

vertical plane that chops one of the methyl groups in
half), so it is a meso compound. As such, it is achiral
and optically inactive.

(d)

(h) This compound has an internal plane of symmetry,

so it is a meso compound. As such, it is achiral and
optically inactive.

(e)

5.54. In each case, begin by numbering the carbon

5.55.
atoms in the Fischer projection (from top to bottom) and
(a) The compound in problem 5.54a has an internal
then draw the skeleton of a bond-line drawing with the
plane of symmetry, and is therefore a meso compound:
same number of carbon atoms. Then, place the
substituents in their correct locations (by comparing the
numbering system in the Fischer projection with the
numbering system in the bond-line drawing). When
drawing each substituent in the bond-line drawing, you
must decide whether it is on a dash or a wedge. For each
chirality center, make sure that the configuration is the
same as the configuration in the Fischer projection. If
necessary, assign the configuration of each chirality
center in both the Fischer projection and the bond-line
drawing to ensure that you drew the configuration (b) The structures shown in 5.54b and 5.54c are
correctly. With enough practice, you may begin to enantiomers. An equal mixture of these two compounds
notice some trends (rules of thumb) that will allow you is a racemic mixture, which will be optically inactive.
to draw the configurations more quickly.
(c) Yes, this mixture is expected to be optically active,
(a) because the structures shown in 5.54d and 5.54e are not
enantiomers. They are diastereomers, which are not
expected to exhibit equal and opposite rotations.

5.56. With three chirality centers, we would expect eight

stereoisomers (23 = 8), shown below (labeled 1–8).
However, structures 1 and 2 represent one compound (a
meso compound), while structures 3 and 4 also represent
one compound (a meso compound). In addition,
(b) structure 5 is the same as structure 8, while structure 6 is
the same as structure 7 (you might find it helpful to build
molecular models to see this). Structures 5-8 are not
meso structures. The reason for the equivalence of
structures 5 and 8 (and also for the equivalence of 6 and
7) is that the central carbon atom in each of these four
structures is actually not a chirality center. For structures
5-8, changing the “configuration” at the central carbon
atom does not produce a stereoisomer, which proves that
 CHAPTER 5 149

the central carbon atom is not a chirality center in these

cases (see the solution to Problem 5.48 for more on this). 5.58. The following two compounds are enantiomers
In summary, there are only four stereoisomers (structures because they are nonsuperimposable mirror images. You
1, 3, 5, and 6). may find it helpful to construct molecular models to help
visualize the mirror image relationship between these
two compounds.

5.59. This compound has two identical groups (methyl

groups) attached to the same position (shown below).
For this reason, the compound will be superimposable on
its mirror image (once again, molecular models may help
visualize this). Therefore, the compound will be achiral.

5.60.
(a) This compound cannot be completely planar because
steric hindrance prevents the two ring systems from
rotating with respect to each other. The compound is
locked in a particular conformation that is chiral.

(b) This ring system cannot be planar because of steric

hindrance, and must therefore adopt a spiral shape (like a
spiral staircase). The spiral can be right handed or left
5.57. handed, and the relationship between these two forms is
(a) The second compound is 2-methylpentane. If we enantiomeric.
redraw the first compound as a bond-line drawing, rather
than a Newman projection, we see that the first 5.61. The compound is chiral because it is not
compound is 3-methylpentane. superimposable on its mirror image, shown below.

5.62. This compound has a center of inversion, which is

a form of reflection symmetry. As a result, this
compound is superimposable on its mirror image and is
therefore optically inactive.
These two compounds, 2-methylpentane and 3-
methylpentane, have the same molecular formula 5.63. The compound contains three chirality centers,
(C6H14) but different constitution, so they are with the following assignments:
constitutional isomers.

(b) The first compound is trans-1,2-

dimethylcyclohexane:

With three chirality centers, there should be a total of 2 3

= 8 stereoisomers, shown below. Pairs of enantiomers
In contrast, the second compound is cis-1,2- are highlighted together. All other relationships are
dimethylcyclohexane. These compounds are diastereomeric.
stereoisomers, but they are not mirror images of each
other. Therefore, they are diastereomers.
150 CHAPTER 5

chirality centers, we expect 23 = 8 possible

stereoisomers, one of which is the natural product
coibacin B.

5.65.
(a) The product has one chirality center, which can either
have the R configuration or the S configuration, as shown
here.

Solvent %ee %S %R
toluene 24 62 38
tetrahydrofuran 48 74 26
CH3CN 72 86 14 (b) Acetonitrile (CH3CN) is the best choice of solvent
CHCl3 30 65 35 because it results in the highest combination of
CH2Cl2 46 73 27 enantioselectivity (72% ee) and percent yield (55%).
hexane 51 75.5 24.5 While toluene gives the same % yield, enantioselectivity
in this solvent is significantly lower.

5.66.
(a) To draw the enantiomer, we simply redraw the
structure in the problem statement, except that we
replace all dashes with wedges, and all wedges with
dashes, as shown:

5.64.
(a) The following are the prioritization schemes that give
rise to the correct assignment of configuration for each
chirality center. (b) The following compounds are the minor products, as
described in the problem statement.

(b) The total number of possible stereoisomers is 2n

(where n = the number of chirality centers). With three
 CHAPTER 5 151

(d) They are stereoisomers, but they are not mirror

(c) The minor products are nonsuperimposable mirror images of each other. Therefore, they are diastereomers.
images of each other. Therefore, they are enantiomers.

5.67.
The following are two examples of correct answers, where the molecule is viewed from different perspectives.

A suggested approach to this problem:

1) Draw a chair structure of the ring on the right side of the compound.
2) Now, to find an appropriate place to connect the second ring, find two axial positions on adjacent carbons so
that they are down and up when going counterclockwise around the ring, as they are in the wedge and dash
drawing. These are the two bridgehead positions.
3) Draw the second ring (with connecting bonds equatorial to the first ring).
4) Replace appropriate methylene groups in the rings with oxygen atoms.
5) Draw all substituents.
5.68.
(a) The compound exhibits rotational symmetry, because it possesses an axis of symmetry (consider rotating the
molecule 180º about this vertical axis). You might find it helpful to construct a molecular model of this compound.

(b) The compound lacks reflectional symmetry; it does not have a plane of symmetry.
(c) Chirality is not dependent on the presence or absence of rotational symmetry. It is only dependent on the presence
or absence of reflectional symmetry. This compound lacks reflectional symmetry and is therefore chiral. That is, it has
a non-superimposable mirror image, drawn here:
152 CHAPTER 5

5.69. Notice that the two groups connected to the front carbon
(a) In the following Newman projection, the front carbon atom are twisted 90º with respect to the two groups
atom is connected to only two groups, and the back connected to the back carbon atom. This is because the
carbon atom is also connected to only two groups: central carbon atom (in between the front carbon atom
and the back carbon atom) is sp hybridized – it has two p
orbitals, which are 90º apart from each other. One p
orbital is being used to form one π bond, while the other
p orbital is being used to form the other π bond.

(b) To draw the enantiomer, we could either switch the two groups connected to the front carbon atom, or we could
switch the two groups connected to the back carbon atom. The former is shown here, in both bond-line format and in a
Newman projection.

(c) To draw a diastereomer of the original compound, simply convert the trans configuration of the alkene to a cis
configuration. The two diastereomers (both cis alkenes) are enantiomers of each other.

5.70.
(a) Glucuronolactone 1L is the enantiomer of 1D, which is shown in the problem statement. To draw the enantiomer of
1D, we simply redraw it, except that we replace all dashes with wedges, and all wedges with dashes, as shown:
 CHAPTER 5 153

(b) There are 5 chirality centers, so there are 32 (or 2 5) possible stereoisomers.

(c)

(d) The four products that are accessible from either of the reactants are the four products shown on the right in the
solution to part c, as indicated above. Recall that the synthetic protocol allows for control of configurations at C2, C3
and C5, but not at C4. Therefore, in order for a specific stereoisomer to be accessible from either 1D or from 1L, that
stereoisomer must display a specific feature. To understand this feature, we must draw one of the ten stereoisomers
and then redraw it again after rotating it 180 degrees about a vertical axis. For example, let’s do this for one of the
meso compounds:

Now we look at the configuration of the chirality center in the bottom right corner of each drawing above (highlighted
in gray). Notice that they have opposite configuration. This is the necessary feature that enables this compound to be
accessible from either 1D or from 1L. Here is another example:
154 CHAPTER 5

Once again, this stereoisomer will be accessible from either 1D or from 1L. In contrast, the first six structures (in the
answer to part c) do not have this feature. For example, consider the first structure: let’s draw it, rotate it 180 degrees,
and then inspect the configuration in the bottom right corner of each drawing:

Note that in this case, the configuration in the bottom right corner of each drawing of this structure is the same.
Therefore, this stereoisomer can ONLY be made from 1D. It cannot be made from 1L. A similar analysis for the first
six stereoisomers (in the answer to part c) shows that all six of these stereoisomers require a specific enantiomer for the
starting material. Only the last four stereoisomers can be made from either 1D or from 1L.

5.71. <AQ> Question is from 3 rd edition. <AQ>