Problem Set on 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. racemates f. meso compounds

b. chirality center g. optically active
c. chirality h. prochirality center
d. diastereomers i. optically inactive
e. enantiomers j. achiral

1. ____ describes organic molecules which rotate plane-polarized light.

Answer: g

2. is the property of “handedness”; the property of an object that causes it to be nonsuperimposable on

its mirror image.

Answer: c

3. are stereoisomers that are not mirror images.

Answer: d

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

Answer: b

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

Answer: f

6. _____ 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:

a. R
b. S
c. 
d.  D

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

8.
COOH

HO OH
prostacyclin

Answer:

COOH

O
* *

*
* *

HO OH

9.
CH3O

O
N
H H
CH3
HO
H codiene

Answer:
CH3O

O
*
* * * N
H H
* CH3
HO
H
10.
OH

NHCH3
ephedrine

Answer:
OH

* *

NHCH3

11. C6H5CHCNH S
NH2
N
O CH3
cephalexin CO2H

Answer:
O
*
C6H5CHCNH S
NH2 * *
N
O CH3

CO2H

12.
O
HO
H3C CCH2OH
HO

H3C CH3

O betamethasone
Answer:
O
HO
H3C CCH2OH
HO
* * *
H3C * CH3
* *
*
*
F

13. COOH
O

O
thromboxane A2 OH

Answer:
* COOH
O *
* *
O *

OH

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

14. OH
15. COOH
HO H
CH2NH2 C
H2N CH3
HO H
norepinephrine alanine

O
16. 17. H 18.
HO2C OH
H H CH3
H2C
H
HO CO2H
CH2
tartaric acid dihydrocarvone

14. The configuration of this carbon atom is .

Answer: R

15. The configuration of this carbon atom is .

Answer: S
16. The configuration of this carbon atom is .

Answer: R

17. The configuration of this carbon atom is .

Answer: S

18. The configuration of this carbon atom is .

Answer: S

Consider the structure of streptimidone to answer the following questions.

O NH
H OH

* * O
H3C H streptimidone

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

Answer:
O

O NH
H OH
S
* * O
R
H3C H

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.

Answer: 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.
Label each pair of stereoisomers below as:

a. enantiomers
b. diastereomers
c. identical

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

H3C H H3C OH
OH H
22.
HO H
H CH2OH HO CH2OH

Answer: a
CO2H H

23. H HO
HO H2OC CH3
CH3

Answer: c

HO2C

24. HO2C CO2H

Answer: b CO2H

H OH HO H
25. HOH2C CHO OHC CH2OH

H OH HO H H OH HO H

Answer: b

Br Br

26.

H3C Br H3C Br
Answer: c

H CH2CH3
27. C C
CH3CH2 CH3 H CH3
Cl Cl

Answer: a
O O
28. H H

H CH3 H3C H
H2C CH2

CH2 CH2
Answer: b

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

Answer:
Br CH3 H

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
CH3 H

H CH3
Br

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

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

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

+2.32
Answer:  = = +58
D
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
*
B
H2
* Pd/C
CH3CH CHCHCH2CH CHCH3

CH3
A O3, then Zn, HOAc

O O O
*
CH3CH + HCCHCH2CH
CH3
C
Refer to the structure below to answer the following questions.
CO2H

C (S)-(-)-Serine
H NH2
HOH2C

35. (S)-(−)-Serine:

a. is dextrorotatory
b. rotates plane-polarized light in a counterclockwise direction
c. rotates plane-polarized light in a clockwise direction
d. is racemic

Answer: b

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

Answer:
CO2H

C
H2N H
CH2OH
37. Give the complete name of the enantiomer of (S)-(−)-serine.

Answer: (R)-(+)-serine

A natural product having []D = +40.3 has been isolated and purified

38. This information indicates that the natural product:

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

Answer: 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

HO OH or HO
OH

HO HO H HO H
OH

Answer:
CO2H HO H HO H

HO OH or HO
OH

HO HO H HO H
OH

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.
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 O

HOCCH2 COH
aconitase citric acid + isocitric acid
C C
(optically inactive) (optically active)
HOC H

O
aconitic acid

a. HO2CCH2 OH b. HO2CCH2
H
C C C CH2CO2H
H HO
CO2H CO2H
CO2H

c. HO2CCH2 H d. cannot be determined

OH
C C
HO2C
H CO2H

Answer: b

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

41. H H
CO2
2OC

H H
succinate
Answer:
pro-S
H H
CO2
2OC

H H
pro-R
42.
H H
CO2

phenylpyruvate

Answer:
pro-R pro-S
H H
CO2

phenylpyruvate

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

Ph
43. C O
2OC

phenylpyruvate

Answer:
re

Ph
C O
2OC

si

3OPOH2C
44. C O
HOH2C

dihydroxyacetone phosphate

Answer:
si

3OPOH2C
C O
HOH2C
re
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 O O OH
acetoacetate synthase
CH3CCO2 + CH3CH2CCO2 CH3C CCO2 + CO2
thiamine pyrophosphate
CH2CH3
-aceto--hydroxybutyrate

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

addition

-OOC -OOC COCH3

S
C O
OH
H3CH2C H3CH2C