Sei sulla pagina 1di 4

Isomers and Stereochemistry

Nonsuperimposable mirror-image molecules are called


enantiomers. Diastereomers are stereoisomers that are not
enantiomers. Enantiomers have identical physical and
chemical properties; diastereomers have different physical
and chemical properties. An achiral reagent reacts identically with both enantiomers; a chiral reagent reacts differently with each enantiomer. A mixture of equal amounts of
two enantiomers is called a racemic mixture.
The letters R and S indicate the configuration about an
asymmetric center. If one stereoisomer has the R configuration and the other has the S configuration, they are enantiomers; if they both have the R configuration or both have
the S configuration, they are identical.
Chiral compounds are optically active, meaning that
they rotate the plane of polarization of polarized light; achiral compounds are optically inactive. If one enantiomer ro-

tates the plane of polarization clockwise (), its mirror


image will rotate it the same amount counterclockwise () .
Each optically active compound has a characteristic
specific rotation. A racemic mixture is optically inactive.
A meso compound has two or more asymmetric centers
and a plane of symmetry; it is an achiral molecule. A compound with the same four groups bonded to two different
asymmetric centers will have three stereoisomers, a meso
compound, and a pair of enantiomers.
When a reactant that does not have an asymmetric center forms a product with one asymmetric center, the product will be a racemic mixture. Catalytic hydrogenation
adds both hydrogens to the same side of the reactant. An
enzyme-catalyzed reaction forms only one stereoisomer;
an enzyme typically catalyzes the reaction of only one
stereoisomer.

PROBLEMS
30. Which of the following have an asymmetric center?
CHBr2Cl
CH2FCl
CH3CHCl2
CHFBrCl

CH3CH2CHClCH3

31. Disregarding stereoisomers, give the structures of all compounds with molecular formula C5H10. Which ones can exist as
stereoisomers?
32. Draw all possible stereoisomers for each of the following compounds. Indicate if no stereoisomers are possible.
a.
b.
c.
d.

2-bromo-4-methylpentane
2-bromo-4-chloropentane
3-heptene
1-bromo-4-methylcyclohexane

e.
f.
g.
h.

1-bromo-3-chlorocyclobutane
2-iodopentane
3,3-dimethylpentane
3-chloro-1-butene

33. Name the following compounds using R,S and E,Z designations where necessary:
CH(CH3)2
F
I
F
H
a.

C
Cl

b.

C
Br

C
H3C

CH2CH3
H

c.

d.

C
Br

Cl

CH3
C CH CH Cl
2
2
CH3CH2 H

34. Mevacor is used clinically to lower serum cholesterol levels. How many asymmetric centers does it have?
HO

O
O

O
O
CH3
H3C

CH3

Mevacor

35. Draw a diastereomer of the following:


CH3
H

Br

OH

CH3



Isomers and Stereochemistry

36. Indicate whether the following pairs of structures represent identical compounds, enantiomers, diastereomers, or constitutional
isomers:
H
CH3
CH3
H3C
H3C
H
H
CH3
a.
C C
C C
e.
and
and
H
CH3
H
CH3
H
Br
Br
H3C
CH2OH
b.

C
H

CH2CH3
and

CH3
CH2CH3

C
H3C

CH2OH
f.

H
CH2OH

C
Cl

CH2CH3
c.

Cl

CH3
CH2CH3

H3C
g.

and
CH3

and

C CH OH
2
CH3CH2 CH
3

C
H3C

and

C
Br

C
Br

CH3
d.

H H
Cl Cl

and

H 3C

Cl H

C
CH3

CH3
CH3

h.

H Cl

CH3

CH3

and
H3C

37. a. Give the product(s) that would be obtained from the reaction of cis-2-butene with each of the following reagents. If the
products can exist as stereoisomers, show which stereoisomers are formed.
4. CH 3OH + acid
1. HCl
2. H 2O + acid
3. H2, Pt>C
b. How would the product(s) differ if the reactant had been trans-2-butene?
38. Which of the following compounds have an achiral stereoisomer?
a. 2,3-dichlorobutane
b. 2,3-dichloropentane
c. 2,4-dibromopentane

d. 2,3-dibromopentane

39. Draw the stereoisomers of 2,4-dichlorohexane. Indicate pairs of enantiomers and pairs of diastereomers.
40. Give the products of the following reactions. If the products can exist as stereoisomers, show which stereoisomers are formed.
a. 1-butene + HCl
b. cis-2-pentene + HCl
c. 1-ethylcyclohexene + H 2O + acid
41. A solution of an unknown compound (3.0 g of the compound in 20 mL of solution), when placed in a polarimeter tube 2.0 dm
long, was found to rotate the plane of polarization of polarized light 1.8 in a counterclockwise direction. What is the specific
rotation of the compound?
42. Butaclamol is a potent antipsychotic that has been used clinically in the treatment of schizophrenia. How many asymmetric centers
does it have?
OH
C(CH3)3

Butaclamol

43. Which of the following objects are chiral?


a. a mug with DAD written on one side
b. a mug with MOM written on one side
c. a mug with DAD written opposite the handle
d. a mug with MOM written opposite the handle

e.
f.
g.
h.

an automobile
a wheelbarrow
a nail
a screw

44. Explain how R and S are related to (+) and (-) .


45. Draw structures for each of the following:
a. (S)-1-bromo-1-chlorobutane
b. two achiral isomers of 3,4,5-trimethylheptane



Isomers and Stereochemistry

46. The stereoisomer of naproxen that is the active ingredient in Aleve and in several other over-the-counter nonsteroidal antiinflammatory drugs is shown below. Is the active ingredient (R)-naproxen or (S)-naproxen?

CH3
C
COH

CH3O

O
(?)-naproxen

47. Draw all the stereoisomers for each of the following:


a. 1-chloro-3-methylpentane
b. 2,4-dichloroheptane

c. 3,4-dichlorohexane

48. Indicate the configuration of the asymmetric centers in the following:


CH2CH2Br
CH2CH3
HC
3

a.

C
Br

H
CH2CH2CH3

b.

Br

Br

49. Citrate synthase, one of the enzymes in the series of enzyme-catalyzed reactions known as the citric acid cycle, catalyzes the
synthesis of citric acid from oxaloacetic acid and acetyl-CoA. If the synthesis is carried out with acetyl-CoA that has radioactive
carbon (14C) in the indicated position, the isomer shown here is obtained. (Note: 14C has a higher priority than 12C.)
O
HOOCCH2CCOOH
oxaloacetic acid

14

CH2COOH

O
+

citrate synthase

14

CH3CSCoA

C
HO

acetyl-CoA

COOH
CH2COOH

citric acid

a. Which stereoisomer of citric acid is synthesized, R or S?


b. Why is the other stereoisomer not obtained?
c. If the acetyl-CoA used in the synthesis does not contain 14C, will the product of the reaction be chiral or achiral?
50. Chloramphenicol is a broad-spectrum antibiotic that is particularly useful against typhoid fever. What is the configuration of each
of the asymmetric centers?
H

HO
H

CH2OH

NHCCHCl2
O
NO2
chloramphenicol

51. For many centuries, the Chinese have used extracts from a group of herbs known as ephedra to treat asthma. Chemists have been
able to isolate a compound from these herbs, which they named ephedrine, a potent dilator of air passages in the lungs.
CH3
CHCHNHCH3
OH
ephedrine

a. How many stereoisomers are possible for ephedrine?


b. The stereoisomer shown here is the one that is pharmacologically active. What is the configuration of each of the asymmetric
centers?
H
C

HO
H

C NHCH3
CH3



Isomers and Stereochemistry

52. Indicate whether the following pairs of structures represent identical compounds or enantiomers:
CH3
CH2CH3
CH3
CH3
H
H
OH
a. Cl
b. HO
H
H
CH3
C
C
C
C
and
and
C
C
C
C
H
Cl
CH3
H
Cl
H
H
Cl
CH2CH3
CH3
CH3
CH3
53. The following compound has only one asymmetric center. Why, then, does it have four stereoisomers?
CH3CH

CHCHCH3
OH

54. Two stereoisomers are obtained from the reaction of HBr with (S)-4-bromo-1-pentene. One of the stereoisomers is optically active,
and the other is not. Give the structures of the stereoisomers, indicating their configurations, and explain the difference in the
optical properties.
55. Indicate whether the following pairs of structures represent identical compounds, enantiomers, diastereomers, or constitutional
isomers:
a.

c.

and

b.

and

d.

and

and

ANSWERS TO SELECTED PROBLEMS


1. a. CH3CH2CH2OH

CH3CHOH

b. 7

CH3CH2OCH3

CH3

2
CH(CH3)2

d.

CH

3. a. F, G, J, L, N, P, Q, R, S, Z b. A, C, D, H, I, M, O, T, U, V, W, X, Y
4. a, c, and f 6. a, c, and f
7. a.

Br

CH2OH

CH2OH

H
b.

CH3

H 3C

CH2CH2Cl

C
CH3CH2

c.

CH3

CH2CH3

CH3

CH2OH

CH

H3C

H
3

b.

CH(CH3)2

a.

CH2CH2Cl
H3 C

CH3

CH2CH2Br

3
CH2

Cl

CH2CH2CH2Br

CH2CH3

4
CH

C
CH3CH2

H
OH

HO

CH2CH3

OH
b.
2

CH2CH2OH

OH

CH3

3
CH2OH

CH2CH2CH3

C
CH3CH2
c.

H
Br

CH2CH2CH3
C

H
Br

CH2CH3

H H
CH3 CH3

29. a. (R)-malate and (S)-malate b. (R)-malate and (S)-malate



CH3

11. a. R b. R 12. a. (R)-2-bromobutane b. (R)-1,3-dichlorobutane 13. a.


enantiomers b. enantiomers 15. a. levorotatory b. dextrorotatory 16. a. S b. R
c. R d. S 17. +168 18. a. -24 b. 0 19. From the data given, you cannot
determine the configuration. 20. a. enantiomers b. identical compounds
(Therefore, they are not isomers.) c. diastereomers 21. a. 8 b. 28 = 256
23. a. diastereomers b. enantiomers c. identical d. constitutional isomers
24. B 26. the one on the left
CH3
CH3
28. a.

Br

CH(CH3)2
HO

10.

9. a, b, and c

c.

Potrebbero piacerti anche