Chapter 9 Stereochemistry

For the following questions MATCH each definition to a term from the list below. Place the letter of the term
in the blank to the left of the definition.
a.
b.
c.
d.
e.
1.

racemates
chirality center
chirality
diastereomers
enantiomers

is the property of handedness; the property of an object that causes it to be nonsuperimposable on

3.

are stereoisomers that are not mirror images.

4.

is an atom in a molecule that is bonded to four different atoms or groups of atoms.

5.

are molecules which contain chirality centers and a plane of symmetry.

6.

meso compounds
optically active
prochirality center
optically inactive
achiral

____ describes organic molecules which rotate plane-polarized light.

2.

f.
g.
h.
i.
j.

_____ describes an sp3-hybridized atom that can become a chirality center by changing one of its attached
groups.
Answer: h

7.

The specific rotation of a compound is denoted by the symbol:

68

R
S

Chapter 9: Stereochemistry

Place asterisks at all the chirality centers in each molecule below.

COOH

HO

OH
prostacyclin

Answer:
COOH

O
* *
*

HO

OH

9.
CH3O

O
H

CH3

HO
H

codiene

Answer:
CH3O

O
H

*
*

HO

*
H

N
CH3

H
Test Items for McMurrys Organic Chemistry, Seventh Edition

69

10.
OH

NHCH3
ephedrine

Answer:
OH
*

NHCH3

O
C6H5CHCNH

11.

NH2
N

CH3

O
cephalexin

CO2H

Answer:
O
*
C6H5CHCNH

S
* *

NH2

CH3

O
CO2H

12.
H3C

HO

HO

O
CCH2OH
CH3

H3C
F
O

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betamethasone

Chapter 9: Stereochemistry

Answer:
H3C

HO
H3C
*

HO

CCH2OH

*
*

CH3

13.

COOH

O
O
thromboxane A2

OH

Answer:
*
O *
*
O

COOH
*

OH

Assign R, S configurations to each indicated chirality center in the molecules below.

OH

15.

H
CH2NH2

HO

COOH
C

H2N

HO
norepinephrine

CH3

alanine

O
17.

16.
OH

HO2C
H
HO

CH3

CO2H

14. The configuration of this carbon atom is

CH2

dihydrocarvone

15. The configuration of this carbon atom is

18.

H2C

tartaric acid

Answer:

Test Items for McMurrys Organic Chemistry, Seventh Edition

71

16. The configuration of this carbon atom is

17. The configuration of this carbon atom is

18. The configuration of this carbon atom is

Consider the structure of streptimidone to answer the following questions.

H3C

NH

OH
*

O
streptimidone

19. Assign R or S configuration to each chirality center indicated in streptimidone.

H3C

OH
*

NH
O

20. Based on the number of chirality centers, how many stereoisomers of streptimidone are possible?
Answer:

Streptimidone has two chirality centers so there are 22, or 4, possible stereoisomers.

21. Will streptimidone have a meso stereoisomer? Explain your answer.

72

No. Meso compounds are compounds that contain chirality centers, but possess a plane of
symmetry. Because the substituents on the chiral carbons are different in streptimidone it is
impossible for any stereoisomer to have a plane of symmetry.

Chapter 9: Stereochemistry

Label each pair of stereoisomers below as:

enantiomers
diastereomers
identical

Place the letter of the correct answer in the blank to the left of the pair of stereoisomers.
H

H3C

22.

H3C

OH

HO

Answer:

H
HO

CH2OH

HO

Answer:

CH2OH

a
H

CO2H

23.

OH

HO
H2OC

H
CH3

CH3

c
HO2C

24.

HO2C

Answer:

CO2H

CO2H

25.

OH

HOH2C

HO
CHO

OHC

H OH HO H

Answer:

H
CH2OH

OH HO H

b
Br

Br

26.
Br

H3C

Answer:

H3C

Br

c
H

27.
CH3CH2

Answer:

CH2CH3

C
Cl

CH3

C
Cl

CH3

Test Items for McMurrys Organic Chemistry, Seventh Edition

73

O
H

28.

CH3

H
H3C

H2C

CH2
CH2

Answer:

CH2

29. Draw a wedge-dash projection of (2R,3S)-dibromobutane.

Br
H
H3C

Br

30. Draw a Newman projection of the most stable conformation of (2R,3S)-dibromobutane sighting down the
C2-C3 bond.
Answer:
Br
H

CH3
H

CH3
Br

31. (2R,3S)-Dibromobutane is:

optically active.
racemic.
dextrorotatory.
a meso compound.
d

32. The alkane formed by hydrogenation of (S)-4-methyl-1-hexene is optically active while the one formed by
hydrogenation of (S)-3-methyl-1-pentene is not. Explain.
Answer:

74

Each starting alkene is optically active because it contains a stereogenic centera carbon with
four different groups bonded to it. The alkane formed by the hydrogenation of (S)-4-methyl-1hexene is optically because carbon four is still chiral. The product of hydrogenation of (S)-3methyl-1-pentene is not optically active because two of the groups on carbon three are the same
nowthey are ethyl groups.

Chapter 9: Stereochemistry

33. Estriol, a potent estrogenic hormone, has been isolated from the urine of pregnant women. When 40 mg of
estriol is dissolved in 1.0 mL of dioxane and placed in a sample tube with 1 dm path length a rotation of
+2.32 is observed. Calculate the specific rotation for estriol.

Answer:

+2.32
= +58
1 dm 0.040 g mL

34. Compound A, C9 H16 , was found to be optically active. On catalytic reduction over a palladium catalyst, 2
equivalents of hydrogen were absorbed to yield compound B. Ozonolysis of A gave two compounds. One
was identified as acetaldehyde, CH 3CHO . The other compound, C, was an optically active dialdehyde,
C5H8O2 . Formulate the reactions and draw structures for compounds A, B and C.
Answer:
CH3
CH3CH2CH2CHCH2CH2CH2CH3
*

*
CHCHCH
2CH

CH3CH

CHCH3

CH3

H2
Pd/C
O3, then Zn, HOAc
O
CH3CH

*
+ HCCHCH2CH
CH3

C
Refer to the structure below to answer the following questions.
CO2H
H
HOH2C

(S)-(-)-Serine

NH2

35. (S)-()-Serine:
a.
b.
c.
d.

is dextrorotatory
rotates plane-polarized light in a counterclockwise direction
rotates plane-polarized light in a clockwise direction
is racemic

Answer:

36. Draw the enantiomer of (S)-()-serine in a wedge-dash projection.

H
CH2OH

Test Items for McMurrys Organic Chemistry, Seventh Edition

75

37. Give the complete name of the enantiomer of (S)-()-serine.

(R)-(+)-serine

A natural product having []D = +40.3 has been isolated and purified
38. This information indicates that the natural product:
a.
b.
c.
d.
Answer:

is racemic.
does not rotate plane-polarized light.
is levorotatory.
is dextrorotatory.
d

39. Two structures have been proposed for this natural product. Circle the structure that is consistent with the
information presented and briefly explain your choice.
CO2H

HO H HO H

OH

HO

or

HO

OH
HO H

HO
OH

HO H

Answer:
CO2H
HO
HO
OH

OH

HO H HO H
or

HO

OH
HO H

HO H

The information presented indicates that the natural product is optically active. To be optically
active molecules must be chiral - that is, they must not have a plane of symmetry. The cyclic
structure, although is has chirality centers, has a plane of symmetry, indicated by the dashed line
on the structure, and can, therefore, not be optically active. The circled structure has four chirality
centers, and is not symmetric. We would expect it to be optically active.

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Chapter 9: Stereochemistry

40. The enzyme aconitase catalyzes the hydration of the alkene functional group of aconitic acid to give two
products, citric acid and isocitric acid. Isocitric acid is optically active; citric acid is not optically active.
Based on your knowledge of alkene hydration and optical activity, the structure of citric acid is:
O

COH

HOCCH2
C

aconitase

HOC

citric acid

isocitric acid
(optically active)

(optically inactive)

O
aconitic acid

a. HO2CCH2

OH
H
C

c. HO2CCH2

CO2H

CH2CO2H

HO
CO2H

d. cannot be determined

H
OH
C

Answer:

CO2H

HO2C

b. HO2CCH2

C
CO2H

Identify the indicated hydrogens in the following molecules as pro-R or pro-S.

H
CO2

2OC

H
succinate

Answer:
pro-S
H

H
CO2

2OC

H
pro-R

Test Items for McMurrys Organic Chemistry, Seventh Edition

77

42.

H
CO2
O

phenylpyruvate

Answer:
pro-R

pro-S
H

H
CO2
O

phenylpyruvate

Identify the indicated faces in the following molecules as re or si.

43.

Ph
C

2OC

phenylpyruvate

Answer:
re
Ph
C

2OC

si

44.

3OPOH2C

HOH2C
dihydroxyacetone phosphate

Answer:
si
3OPOH2C

HOH2C
re
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Chapter 9: Stereochemistry

45. Acetoacetate synthase catalyzes the addition of pyruvate to -ketobutyrate to yield -aceto-hydroxybutyrate. If the addtion occurs from the si face of -ketobutyrate, what is the stereochemistry of
the product?
O

CH3CCO2

+ CH3CH2CCO2

O
acetoacetate synthase
thiamine pyrophosphate

CH3C

OH
CCO2

CO2

CH2CH3
-aceto--hydroxybutyrate

Answer: Addition of the aceto group to the si face results in the S enantiomer of -aceto-hydroxybutyrate.

addition

-OOC

-OOC

H3CH2C

Test Items for McMurrys Organic Chemistry, Seventh Edition

H3CH2C

COCH3
S
OH

79