5 STEREOCHEMISTRY:

CHIRAL MOLECULES

SOLUTIONS TO PROBLEMS
5.1 (a) Achiral (c) Chiral (e) Chiral (g) Chiral
(b) Achiral (d) Chiral (f) Chiral (h) Achiral

5.2 (a) Yes (b) No (c) No

5.3 (a) They are the same molecule. (b) They are enantiomers.

5.4 (a), (b), (e), (g), and (i ) do not have chirality centers.

CH3 CH3
(c) H C Cl Cl C H

CH2 CH2

CH3 (1) CH3 (2)

CH3 CH3
(d) H C CH2OH HOCH2 C H

CH2 CH2

CH3 (1) CH3 (2)

CH3 CH3
(f) H C Br Br C H

CH2 CH2

CH2 CH2

CH3 (1) CH3 (2)

65
66 STEREOCHEMISTRY: CHIRAL MOLECULES

CH3 CH3

CH2 CH2
(h) H C CH3 H3C C H

CH2 CH2

CH2 CH2

CH3 (1) CH3 (2)

CH3 CH3
(j) H C CH2Cl ClCH2 C H

CH2 CH2

CH3 (1) CH3 (2)

O
5.5 (a) (b)
* N * O
N
O O
H
Limonene Thalidomide

N O
H H N
O O
H
(R) (S )

N O
H H N
O O
H
(S ) (R)
 STEREOCHEMISTRY: CHIRAL MOLECULES 67

OH OH
5.6 (a) O (c) HO O O
* *
*
OH
H HO OH

* OH
(b) HO O (d)
OH * *
*
*
*
HO

5.7 The following items possess a plane of symmetry, and are, therefore, achiral.
(a) A screwdriver
(b) A baseball bat (ignoring any writing on it)
(h) A hammer

5.8 In each instance below, the plane defined by the page is a plane of symmetry.

(a) H (b) H (e) CH3 H

C C C C
H3C H3 C
H CH3
H3C F H3 C CH2CH3

(i) CH3 H
(g) H
C C
C
CH3CH2 CH3 CH2CH3
CH3CH2 CH3

F F
5.9 C C
H H
Br Cl Cl Br

(S ) (R)

5.10 (c) (1) is (S )

(2) is (R)
(d) (1) is (S)
(2) is (R)
68 STEREOCHEMISTRY: CHIRAL MOLECULES

(f) (1) is (S)

(2) is (R)
(h) (1) is (S)
(2) is (R)
(j) (1) is (S)
(2) is (R)

5.11 (a) Cl > SH > OH > H

(b) CH2Br > CH2Cl > CH2OH > CH3

(c) OH > CHO > CH3 > H

(d) C(CH3)3 > CH CH2 > CH(CH3)2 > H

(e) OCH3 > N(CH3)2 > CH3 > H

(f ) OPO3H2 > OH > CHO > H

5.12 (a) (S ) (b) (R ) (c) (S ) (d) (R )

5.13 (a) Enantiomers

(b) Two molecules of the same compound
(c) Enantiomers

5.14
O O

H H

(S )-(+)-Carvone (R)-(−)-Carvone

observed specific rotation

5.15 (a) Enant. excess = × 100
specific rotation of pure enantiomer
+1.151
= × 100
+5.756
= 20.00%
(b) Since the (R) enantiomer (see Section 5.8C) is +, the (R) enantiomer is present in
excess.
 STEREOCHEMISTRY: CHIRAL MOLECULES 69

O O
(a) C OH (b) CH3 C OH
5.16
HO CH2 C CH3 C C

CH3 NH2 SH H NH2

HO
(S )-Methyldopa (S )-Penicillamine

O
(c) CH3 C OH
CH3 C CH2 C

H H CH3

(S )-Ibuprofen

5.17

HO H

(R) configuration

5.18 O

O
N

(R)
(S)

5.19 (a) Diastereomers.

(b) Diastereomers in each instance.
(c) No, diastereomers have different melting points.
(d) No, diastereomers have different boiling points.
(e) No, diastereomers have different vapor pressures.
70 STEREOCHEMISTRY: CHIRAL MOLECULES

STUDY AID
An Approach to the Classification of Isomers
We can classify isomers by asking and answering a series of questions:

Do the compounds have the

same molecular formula?

Yes No
Are they different? They are not isomers.

Yes No
They are isomers. They are identical.

Do they differ in connectivity?

Yes No
They are constitutional They are stereoisomers.
isomers.

Are they mirror images

of each other?

Yes No
They are enantiomers. They are diastereomers.

5.20 (a) It would be optically active.

(b) It would be optically active.
(c) No, because it is a meso compound.
(d) No, because it would be a racemic form.

5.21 (a) Represents A

(b) Represents C
(c) Represents B
 STEREOCHEMISTRY: CHIRAL MOLECULES 71

5.22 (a) H Cl Cl H H Cl

H Cl Cl H Cl H
(1) (2) (3)

Enantiomers Meso compound

(b)
H HO H H
HO OH H H OH HO H OH
(1) (2) (3)

Enantiomers Meso compound

H F F H H F
Cl Cl Cl
(c) Cl Cl Cl
H F F H F H
(1) (2) (3)

Enantiomers Meso compound

(d)
H Cl
H OH Cl HO H H H OH H Cl HO H Cl H
(1) (2) (3) (4)

Enantiomers Enantiomers

H F F H F H H F
(e)

H Br Br H H Br Br H
(1) (2) (3) (4)

Enantiomers Enantiomers
72 STEREOCHEMISTRY: CHIRAL MOLECULES

H OH HO H
(f ) HO2C HO2C
CO2H CO2H
H OH HO H
(1) (2)

Enantiomers

HO H
HO2C
CO2H
H OH
(3)
Meso compound

5.23 B is (2S,3S)-2,3-Dibromobutane
C is (2R,3S)-2,3-Dibromobutane

5.24 (a) (1) is (2S,3S)-2,3-Dichlorobutane

(2) is (2R,3R)-2,3-Dichlorobutane
(3) is (2R,3S)-2,3-Dichlorobutane
(b) (1) is (2S,4S)-2,4-Pentanediol
(2) is (2R,4R)-2,4-Pentanediol
(3) is (2R,4S)-2,4-Pentanediol
(c) (1) is (2R,3R)-1,4-Dichloro-2,3-difluorobutane
(2) is (2S,3S)-1,4-Dichloro-2,3-difluorobutane
(3) is (2R,3S)-1,4-Dichloro-2,3-difluorobutane
(d) (1) is (2S,4S)-4-Chloro-2-pentanol
(2) is (2R,4R)-4-Chloro-2-pentanol
(3) is (2S,4R)-4-Chloro-2-pentanol
(4) is (2R,4S)-4-Chloro-2-pentanol
(e) (1) is (2S,3S)-2-Bromo-3-fluorobutane
(2) is (2R,3R)-2-Bromo-3-fluorobutane
(3) is (2S,3R)-2-Bromo-3-fluorobutane
(4) is (2R,3S)-2-Bromo-3-fluorobutane
(f) (1) is (2R,3R)-Butanedioic acid
(2) is (2S,3S)-Butanedioic acid
(3) is (2R,3S)-Butanedioic acid
 STEREOCHEMISTRY: CHIRAL MOLECULES 73

5.25 NO2

HO H
C

H C NHCOCHCl2
CH2OH
Chloramphenicol

5.26 (a) A C1, R; C2, R

B C1, S; C2, S

(b,c) CH3

H Br
optically inactive, a meso compound
H Br

CH3
C

5.27 (a) No (b) Yes (c) No (d) No (e) Diastereomers

(f) Diastereomers

5.28 Me Me Me H H Me

H H H Me Me H
Meso compound
Enantiomers
74 STEREOCHEMISTRY: CHIRAL MOLECULES

H Cl
5.29 (a)
= (1R,2R)
Br Cl H H
H Br Br Cl
Enantiomers
H Cl (both trans)
Br Cl
Br Cl H H
= (1S,2S)

H Br

H H

= (1R,2S)
Br H H Cl
Cl Br Br Cl
Enantiomers
H H (both cis)
H Cl Br Cl
Br H
= (1S,2R)
Cl Br

(b) H
H H Cl
Cl
= (1S,3R)
H
Br
Cl
Br Br Enantiomers
Cl (both cis)
Br Cl Cl
H
= (1R,3S )
Br
H H
H Br
Cl
H Cl Cl
H
= (1S,3S )
H
Br
H
Br Br Enantiomers
H (both trans)
Br H Cl
Cl
= (1R,3R)
Br
H Cl
H Br
 STEREOCHEMISTRY: CHIRAL MOLECULES 75

H Br
(c)
Cl H
Br H = Br Cl
H Cl
Achiral (trans)

Cl Br
H H
Br Cl = Br Cl
H H
Achiral (cis)

5.30 See Problem 5.29. The molecules in (c) are achiral, so they have no (R, S ) designation.

5.31 HO H HO H
O HgO O HNO2
HO HO (S )-(−)-Isoserine
H2O (see the following
H OH reaction also)
(S)-(−)-Glyceraldehyde (S)-(+)-Glyceric acid

HO H HO H HO H
O HNO2 O Zn O
H2N Br
HBr H3O+
OH OH OH
(S )-(−)-Isoserine (R)-(+)-3-Bromo- (S )-(+)-Lactic acid
2-hydroxypropanoic
acid

CHO CHO
R S
5.32 (a) H OH HO H

CH2OH CH2OH
(R)-Glyceraldehyde (S )-Glyceraldehyde

CO2H CO2H
R S
H OH HO H
(b) R S
HO H H OH

CO2H CO2H
(+)-Tartaric acid (−)-Tartaric acid
76 STEREOCHEMISTRY: CHIRAL MOLECULES

CO2H CO2H
R S
(c) H OH HO H

CH3 CH3
(R)-Lactic acid (S)-Lactic acid

Problems

Chirality and Stereoisomerism

5.33 (a), (b), (f), and (g) only

5.34 (a) Seven.

(b) (R)- and (S)-3-Methylhexane and (R)- and (S)-2,3-dimethylpentane.

S S R
Cl F Cl H2N Cl F SH
5.35
SH
Br Br
R S S S S
Cl S

H
H H H H O H
5.36 H N Me
O
H H Me Me
O H
H
H
(R) configuration

5.37 (a) (b) Two, indicated by asterisks in (a)

Cl

Cl
(c) Four
(d) Because a trans arrangement of the one carbon bridge is structurally impossible. Such
a molecule would have too much strain.
 STEREOCHEMISTRY: CHIRAL MOLECULES 77

5.38 (a) A is (2R,3S)-2,3-dichlorobutane; B is (2S,3S)-2,3-dichlorobutane; C is (2R,3R)-2,3-

dichlorobutane.
(b) A

CH3
CH3
CH2CH3
CH3 etc.
5.39 (a) or or

(b) and or CH2 and CH2

CH3 CH3
CH3 H3C CH3 CH3 CH3 CH
3

(other answers are possible)

(c) and
CH3
CH3 CH3
CH3 (other answers are possible)

CH3 CH3
(d) and
C C
H H
CH CH2 CH2 CH
CH3CH2 CH2CH3

(e) H3C CH2CH2CH3 H 3C H

C C and C C
H H H CH2CH2CH3
(other answers are possible)

5.40 (a) Same: (S)

(b) Enantiomers: left (S); right (R)
(c) Diastereomers: left (1S, 2S); right (1R, 2S)
(d) Same: (1S, 2S)
(e) Diastereomers: left (1S, 2S); right (1S, 2R)
(f) Constitutional isomers: both achiral
(g) Diastereomers: left, cis (4S); right, trans (4R)
(h) Enantiomers: left (1S, 3S); right (1R, 3R)
(i) Same: no chirality centers
78 STEREOCHEMISTRY: CHIRAL MOLECULES

(j) Different conformers of the same molecule (interconvertable by a ring flip): (1R, 2S)
(k) Diastereomers: left (1R, 2S); right (1R, 2R)
(l) Same: (1R, 2S)
(m) Diastereomers: no chirality center in either
(n) Constitutional isomers: no chirality center in either
(o) Diastereomers: no chirality center in either
(p) Same: no chirality center
(q) Same: no chirality center
5.41 All of these molecules are expected to be planar. Their stereochemistry is identical to that of
the corresponding chloroethenes. (a) can exist as cis and trans isomers. Only one compound
exists in the case of (b) and (c).
5.42 (a) diastereomers (c) enantiomers
(b) enantiomers (d) same compound

5.43 H H
CH2 C CH2CH3 CH2 C CH2CH3
C C
CH3 H H CH3
D (racemic)
CH3CH2 CH2CH3
C
CH3 H
E (achiral)

5.44 CH3 CH3 H2

C C C CH3CH2CH2CH2CH3
Pd, Pt, or Ni
H H pressure
(or enantiomer) (achiral)
F G

5.45 CH3 CH3

H2
Pd, Pt, or Ni
pressure
(or enantiomer) (achiral)
H I
or
CH2CH3 CH2CH3
H2
Pd, Pt, or Ni
pressure
(or enantiomer) (achiral)
 STEREOCHEMISTRY: CHIRAL MOLECULES 79

5.46
(S )
Ο
+
H3N O
N CH3
H
− Ο
O
(S)
Ο
Aspartame

CH3 CH3

5.47 (a) CH3

CH3

(1) CH3 (2) CH3 (3) CH3 (4) CH3

(b) (3) and (4) are chiral and are enantiomers of each other.
(c) Three fractions: a fraction containing (1), a fraction containing (2), and a fraction
containing (3) and (4) [because, being enantiomers, (3) and (4) would have the same
vapor pressure].
(d) None

R S

Cl S Cl S
S R

5.48 Br CH3 H3C

Br
Diastereomer Enantiomer
(one center changed) (mirror image)
all centers changed

H H
5.49 (a)
Et Et
Et Et
H H
(b) No, they are not superposable.
(c) No, and they are, therefore, enantiomers of each other.
Et Et
(d)
H H
Et Et
H H
80 STEREOCHEMISTRY: CHIRAL MOLECULES

(e) No, they are not superposable.

(f) Yes, and they are, therefore, just different conformations of the same molecule.

5.50 (a) H H

Et Et Et
Et
H H
(b) Yes, and, therefore, trans-1,4-diethylcyclohexane is achiral.
(c) No, they are different orientations of the same molecule.
(d) Yes, cis-1,4-diethylcyclohexane is a stereoisomer (a diastereomer) of trans-1,
4-diethylcyclohexane.
Et

Et H
H
cis-1,4-Diethylcyclohexane

(e) No, it, too, is superposable on its mirror image. (Notice, too, that the plane of the page
constitutes a plane of symmetry for both cis-1,4-diethylcyclohexane and for trans-1,
4-diethylcyclohexane as we have drawn them.)

5.51 trans-1,3-Diethylcyclohexane can exist in the following enantiomeric forms.

Et Et

H H
H H
Et Et
trans-1,3-Diethylcyclohexane enantiomers

cis-1,3-Diethylcyclohexane consists of achiral molecules because they have a plane of

symmetry. [The plane of the page (below) is a plane of symmetry.]
Et

Et
HH
cis-1,3-Diethylcyclohexane (meso)
 STEREOCHEMISTRY: CHIRAL MOLECULES 81

Challenge Problems

5.52 (a) Since it is optically active and not resolvable, it must be the meso form:

CO2H (b) CO2H CO2H

H OH H OH HO C H
C C

C C C
H OH HO H H OH
CO2H CO2H CO2H
(meso) (R, R) (S, S)

(c) No (d) A racemic mixture

−30
5.53 (a) [α]D = = −300
(0.10 g/mL)(1.0 dm)
+165
(b) [α]D = = +3300
(0.05 g/mL)(1.0 dm)
The two rotation values can be explained by recognizing that this is a powerfully optically
active substance and that the first reading, assumed to be −30, was really +330. Making
this change the [α]D becomes +3300 in both cases.
(c) No, the apparent 0 rotation could actually be + or −360 (or an integral multiple of these
values).

5.54 Yes, it could be a meso form or an enantiomer whose chirality centers, by rare coincidence,
happen to cancel each other’s activities.

5.55 A compound C3 H6 O2 has an index of hydrogen deficiency of 1. Thus, it could possess a

carbon-carbon double bond, a carbon-oxygen double bond, or a ring.
The IR spectral data rule out a carbonyl group but indicate the presence of an —OH
group.
No stable structure having molecular formula C3 H6 O2 with a C C bond can exist in
stereoisomeric forms but 1,2-cyclopropanediol can exist in three stereoisomeric forms.
Only ethylene oxide (oxirane) derivatives are possible for Y.
CH2OH HOCH2

O O
82 STEREOCHEMISTRY: CHIRAL MOLECULES

QUIZ
5.1 Describe the relationship between the two structures shown.
CH3 H
H C Br CH3 C Br

Cl Cl

(a) Enantiomers (b) Diastereomers (c) Constitutional isomers

(d) Conformations (e) Two molecules of the same compound

5.2 Which of the following molecule(s) possess(es) a plane of symmetry?

H
F F
(a) H Cl (b) F Cl (c) Cl
C C
Br
Br Br H
(d) More than one of these (e) None of these

5.3 Give the (R, S) designation of the structure shown:

O CH3
C H
HO C

Cl

(a) (R) (b) (S) (c) Neither, because this molecule has no chirality center.
(d) Impossible to tell

5.4 Select the words that best describe the following structure:

CH3
H C Cl

C
H Cl
CH3

(a) Chiral (b) Meso form (c) Achiral (d) Has a plane of symmetry
(e) More than one of these
 STEREOCHEMISTRY: CHIRAL MOLECULES 83

5.5 Select the words that best describe what happens to the optical rotation of the alkene shown
when it is hydrogenated to the alkane according to the following equation:
H H
CH3CH2 CH3 Ni CH3CH2 CH3
C H2 pressure
C

(R) CH CH2 CH2CH3

(a) Increases (b) Changes to zero (c) Changes sign

(d) Stays the same (e) Impossible to predict

5.6 There are two compounds with the formula C7 H16 that are capable of existing as enan-
tiomers. Write three-dimensional formulas for the (S) isomer of each.

5.7 Compound A is optically active and is the (S ) isomer.

H2
CH3CHCH2CH3
Ni
pressure CH2CH3

5.8 Compound B is a hydrocarbon with the minimum number of carbon atoms necessary for
it to possess a chirality center and, as well, alternative stereochemistries about a double bond.

B
84 STEREOCHEMISTRY: CHIRAL MOLECULES

5.9 Which is untrue about the following structure?

Cl

Cl

(a) It is the most stable of the possible conformations.

(b) µ = 0 D
(c) It is identical to its mirror image.
(d) It is optically active.
(e) (R,S ) designations cannot be applied.

5.10 CH2OH is a Fischer projection of one of stereoisomers.

H C OH

HO C H

H C OH

CH3

(a) 2 (b) 3 (c) 4 (d) 7 (e) 8