CHAPTER 7
STEREOCHEMISTRY
SOLUTIONS TO TEXT PROBLEMS
7.1 (c) Carbon-2 is a stereogenic center in 1-bromo-2-methylbutane, as it has four different
substituents: H, CH
3
, CH
3
CH
2
, and BrCH
2
.
(d) There are no stereogenic centers in 2-bromo-2-methylbutane.
7.2 (b) Carbon-2 is a stereogenic center in 1,1,2-trimethylcyclobutane.
1,1,3-Trimethylcyclobutane however, has no stereogenic centers.
CH
3
H
3
C
H
3
C H
Not a stereogenic center;
two of its substituents are the same.
CH
3
CH
3
H
H
3
C
A stereogenic center; the four substituents to which
it is directly bonded [H, CH
3
, CH
2
, and C(CH
3
)
2
]
are all different from one another.
CH
3
CH
2
CH
3
C
CH
3
Br
BrCH
2
CH
2
CH
3
C
CH
3
H
156
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7.3 (b) There are two planes of symmetry in (Z)-1,2-dichloroethene, of which one is the plane of the
molecule and the second bisects the carbon–carbon bond. There is no center of symmetry. The
molecule is achiral.
(c) There is a plane of symmetry in cis-1,2-dichlorocyclopropane that bisects the C-1@C-2 bond
and passes through C-3. The molecule is achiral.
(d) trans-1,2-Dichlorocyclopropane has neither a plane of symmetry nor a center of symmetry. Its
two mirror images cannot be superposed on each other. The molecule is chiral.
7.4 The equation relating specific rotation [H9251] to observed rotation H9251 is
[H9251] H11005
The concentration c is expressed in grams per 100 mL and the length l of the polarimeter tube in
decimeters. Since the problem specifies the concentration as 0.3 g/15 mL and the path length as
10 cm, the specific rotation [H9251] is:
[H9251]
H11005
H11005 H1100239°
7.5 From the previous problem, the specific rotation of natural cholesterol is [H9251] H11005 H1100239°. The mixture
of natural (H11002)-cholesterol and synthetic (H11001)-cholesterol specified in this problem has a specific
rotation [H9251] of H1100213°.
Optical purity H11005 %(H11002)-cholesterol H11002 % (H11001)-cholesterol
33.3% H11005 %(H11002)-cholesterol H11002 [100 H11002 %(H11002)-cholesterol]
133.3% H11005 2 [% (H11002)-cholesterol]
66.7% H11005 % (H11002)-cholesterol
The mixture is two thirds natural (H11002)-cholesterol and one third synthetic (H11001)-cholesterol.
100(H110020.78°)
H5007H5007H5007H5007
100(0.3 gH2086215 mL)(10 cmH2086210 cm/dm)
100H9251
H5007
cl
Cl H H Cl
H Cl
and are nonsuperposable
mirror images
Cl H
Cl
H
Cl
H
1 2
3
Plane of symmetry
CC
ClCl
H
H
Planes of symmetry
STEREOCHEMISTRY 157
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158 STEREOCHEMISTRY
7.6 Draw the molecular model so that it is in the same format as the drawings of (H11001) and (H11002)-2-butanol
in the text.
Reorient the molecule so that it can be compared with the drawings of (H11001) and (H11002)-2-butanol.
The molecular model when redrawn matches the text’s drawing of (H11001)-2-butanol.
7.7 (b) The solution to this problem is exactly analogous to the sample solution given in the text to
part (a).
Order of precedence: CH
2
F H11022 CH
3
CH
2
H11022 CH
3
H11022 H
The lowest ranked substituent (H) at the stereogenic center points away from us in the
drawing. The three higher ranked substituents trace a clockwise path from CH
2
FtoCH
2
CH
3
to CH
3
.
The absolute configuration is R; the compound is (R)-(H11001)-1-fluoro-2-methylbutane.
(c) The highest ranked substituent at the stereogenic center of 1-bromo-2-methylbutane is CH
2
Br,
and the lowest ranked substituent is H. Of the remaining two, ethyl outranks methyl.
Order of precedence: CH
2
Br H11022 CH
2
CH
3
H11022 CH
3
H11022 H
The lowest ranking substituent (H) is directed toward you in the drawing, and therefore the
molecule needs to be reoriented so that H points in the opposite direction.
H
CH
3
BrCH
2
CH
2
CH
3
(H11001)-1-Bromo-2-methylbutane
turn 180H11034
C
CH
3
H
CH
2
Br
CH
3
CH
2
C
C
H
3
C CH
2
F
CH
2
CH
3
C
H
H
3
C
CH
2
F
CH
3
CH
2
(H11001)-1-Fluoro-2-methylbutane
which becomesReorient
H
3
C CH
2
CH
3
C
HO
H H
OH
H
3
C
CH
3
CH
2
C
H
H
H
3
C CH
2
CH
3
C
HO H
O
C
C
C
H
H H
H
H
H
H
C
H
Redraw as
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The three highest ranking substituents trace a counterclockwise path when the lowest ranked
substituent is held away from you.
The absolute configuration is S, and thus the compound is (S)-(H11001)-1-bromo-2-methylbutane.
(d) The highest ranked substituent at the stereogenic center of 3-buten-2-ol is the hydroxyl group,
and the lowest ranked substituent is H. Of the remaining two, vinyl outranks methyl.
Order of precedence: HO H11022 CH
2
?CH H11022 CH
3
H11022 H
The lowest ranking substituent (H) is directed away from you in the drawing. We see that the
order of decreasing precedence appears in a counterclockwise manner.
The absolute configuration is S, and the compound is (S)-(H11001)-3-buten-2-ol.
7.8 (b) The stereogenic center is the carbon that bears the methyl group. Its substituents are:
When the lowest ranked substituent points away from you, the remaining three must appear in
descending order of precedence in a counterclockwise fashion in the S enantiomer. (S)-1, 1-
difluoro-2-methylcyclopropane is therefore
7.9 (b) The Fischer projection of (R)-(H11001)-1-fluoro-2-methylbutane is analogous to that of the alcohol
in part (a). The only difference in the two is that fluorine has replaced hydroxyl as a sub-
stituent at C-1.
Although other Fischer projections may be drawn by rotating the perspective view in other di-
rections, the one shown is preferred because it has the longest chain of carbon atoms oriented
on the vertical axis with the lowest numbered carbon at the top.
(c) As in the previous parts of this problem, orient the structural formula of (S)-(H11001)-1-bromo-
2-methylbutane so the segment BrCH
2
@C@CH
2
CH
3
is aligned vertically with the lowest
numbered carbon at the top.
C
CH
3
CH
3
CH
2
CH
2
Br
H
CH
3
C
CH
2
CH
3
CH
2
Br
H H
3
C
CH
2
CH
3
CH
2
Br
His the same as which becomes the Fischer projection
C
H
3
C
CH
3
CH
2
CH
2
F
H
C CH
3
CH
2
CH
3
CH
2
F
H CH
3
CH
2
CH
3
CH
2
F
His the same as which becomes the Fischer projection
CH
3
H
F
F
CF
2
CH
2
H11022 CH
2
CF
2
H11022 CH
3
H11022 H
Highest
rank
Lowest
rank
(H11001)-3-Buten-2-ol
CH
2
CH
2
HO
C
H
H
3
C
CH
2
C
H
3
C CH
OH
C
BrCH
2
CH
3
CH
2
CH
3
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(d) Here we need to view the molecule from behind the page in order to write the Fischer projec-
tion of (S)-(H11001)-3-buten-2-ol.
7.10 In order of decreasing rank, the substituents attached to the stereogenic center in lactic acid are
@OH, @CO
2
H, @CH
3
, and @H. The Fischer projection given for (H11001)-lactic acid (a) corresponds
to the three-dimensional representation (b), which can be reoriented as in (c). When (c) is viewed
from the side opposite the lowest ranked substituent (H), the order of decreasing precedence is anti-
clockwise, as shown in (d). (H11001)-Lactic acid has the S configuration.
7.11 The erythro stereoisomers are characterized by Fischer projections in which analogous substituents,
in this case OH and NH
2
, are on the same side when the carbon chain is vertical. There are two
erythro stereoisomers that are enantiomers of each other:
Analogous substituents are on opposite sides in the threo isomer:
7.12 There are four stereoisomeric forms of 3-amino-3-butanol:
(2R,3R) and its enantiomer (2S,3S)
(2R,3S) and its enantiomer (2S,3R)
In the text we are told that the (2R,3R) stereoisomer is a liquid. Its enantiomer (2S,3S) has the same
physical properties and so must also be a liquid. The text notes that the (2R,3S) stereoisomer is a
solid (mp 49°C). Its enantiomer (2S,3R) must therefore be the other stereoisomer that is a crystalline
solid.
CH
3
OH
H
CH
3
H
H
2
N
Threo
CH
3
H
NH
2
CH
3
HO
H
Threo
CH
3
OH
NH
2
CH
3
H
H
Erythro
CH
3
H
H
CH
3
HO
H
2
N
Erythro
H
3
C
HO
CO
2
H
HC
(c)
CH
3
HO
CO
2
H
H
(b)
CH
3
HO
CO
2
H
H
(a)
CH
3
OHHO
2
C
(d)
C
C
CH
3
HO
CH CH
2
CH CH
2
CH CH
2
H
C OH
CH
3
H OH
CH
3
His the same as which becomes the Fischer projection
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7.13 Examine the structural formula of each compound for equivalently substituted stereogenic centers.
The only one capable of existing in a meso form is 2,4-dibromopentane.
None of the other compounds has equivalently substituted stereogenic centers. No meso forms are
possible for:
7.14 There is a plane of symmetry in the cis stereoisomer of 1,3-dimethylcyclohexane, and so it is an
achiral substance—it is a meso form.
The trans stereoisomer is chiral. It is not a meso form.
7.15 A molecule with three stereogenic centers has 2
3
, or 8, stereoisomers. The eight combinations of R
and S stereogenic centers are:
Stereogenic center Stereogenic center
1 2 3 1 2 3
Isomer 1 R R R Isomer 5 SSS
Isomer 2 R R S Isomer 6 SSR
Isomer 3 R S R Isomer 7 SRS
Isomer 4 S R R Isomer 8 RSS
7.16 2-Hexuloses have three stereogenic centers. They are marked with asterisks in the structural
formula.
No meso forms are possible, and so there are a total of 2
3
, or 8, stereoisomeric 2-hexuloses.
HOCH
2
CCHCHCHCH
2
OH
OH
O
OH
OH
**
*
CH
3
H
3
C
1
35
4
26
Plane of symmetry passes through
C-2 and C-5 and bisects the ring.
2,3-Dibromopentane
CH
3
CHCHCH
2
CH
3
Br Br
4-Bromo-2-pentanol
CH
3
CHCH
2
CHCH
3
OH Br
3-Bromo-2-pentanol
CH
3
CHCHCH
2
CH
3
OH
Br
2,4-Dibromopentane
Equivalently substituted
stereogenic centers
CH
3
CHCH
2
CHCH
3
Br
*
Br
*
CH
3
Br
H
CH
3
H
H
BrH
Fischer projection of
meso-2,4-dibromopentane
Plane of
symmetry
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7.17 Epoxidation of (Z)-2-butene gives the meso (achiral) epoxide. Oxygen transfer from the peroxy acid
can occur at either face of the double bond, but the product formed is the same because the two
mirror-image forms of the epoxide are superposable.
Epoxidation of (E)-2-butene gives a racemic mixture of two enantiomeric epoxides.
7.18 The observed product mixture (68% cis-1,2-dimethylcyclohexane: 32% trans-1,2-dimethylcyclo-
hexane) contains more of the less stable cis stereoisomer than the trans. The relative stabilities of the
products therefore play no role in determining the stereoselectivity of this reaction.
7.19 The tartaric acids incorporate two equivalently substituted stereogenic centers. (H11001)-Tartaric acid, as
noted in the text, is the 2R,3R stereoisomer. There will be two additional stereoisomers, the enan-
tiomeric (H11002)-tartaric acid (2S,3S) and an optically inactive meso form.
7.20 No. Pasteur separated an optically inactive racemic mixture into two optically active enantiomers. A
meso form is achiral, is identical to its mirror image, and is incapable of being separated into opti-
cally active forms.
(2S,3S)-Tartaric acid
(optically active)
(mp 170°C, [H9251]
D
H11002 12°)
meso-Tartaric acid
(optically inactive)
(mp 140°C)
CO
2
H
CO
2
H
HO
OHH
H H
H
CO
2
H
CO
2
H
OH
OH
Plane of symmetry
O
CH
3
CH
3
H
H
S
S
(2S,3S)-2,3-Epoxybutane
O
H
3
C
H
3
C
H
H
R
R
(2R,3R)-2,3-Epoxybutane
CH
3
COOH
O
CH
3
COOH
O
H
CH
3
H
E
H
3
C
C
C
O
CH
3
CH
3
H
H
S
R
meso-2,3-Epoxybutane
O
H
3
C
H
3
C
H
H
R
S
meso-2,3-Epoxybutane
H
3
C
CH
3
H
Z
H
C
C
CH
3
COOH
O
CH
3
COOH
O
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7.21 The more soluble salt must have the opposite configuration at the stereogenic center of
1-phenylethylamine, that is, the S configuration. The malic acid used in the resolution is a single
enantiomer, S. In this particular case the more soluble salt is therefore (S)-1-phenylethylammonium
(S)-malate.
7.22 In an earlier exercise (Problem 4.23) the structures of all the isomeric C
5
H
12
O alcohols were pre-
sented. Those that lack a stereogenic center and thus are achiral are
The chiral isomers are characterized by carbons that bear four different groups. These are:
7.23 The isomers of trichlorocyclopropane are
7.24 (a) Carbon-2 is a stereogenic center in 3-chloro-1,2-propanediol. Carbon-2 has two equivalent
substituents in 2-chloro-1,3-propanediol, and is not a stereogenic center.
(b) The primary bromide is achiral; the secondary bromide contains a stereogenic center and is
chiral.
CH
3
CH CHCH
2
Br
Achiral
CH
3
CHCH CH
2
*
Br
Chiral
ClCH
2
CHCH
2
OH
*
OH
3-Chloro-1,2-propanediol
Chiral
HOCH
2
CHCH
2
OH
Cl
2-Chloro-1,3-propanediol
Achiral
cis-1,2,3-Trichlorocyclopropane
(achiral—contains a plane of symmetry)
Cl
HH
Cl
Cl
trans-1,2,3-Trichlorocyclopropane
(achiral—contains a plane of symmetry)
Cl
HH
Cl
Cl
Cl
HCl
Cl Cl
H
Cl
Enantiomeric forms of 1,1,2-trichlorocyclopropane
(both chiral)
Cl
3-Methyl-2-butanol2-Pentanol
CH
3
CHCH
2
CH
2
CH
3
OH
*
2-Methyl-1-butanol
CH
3
CH
2
CHCH
2
OH
CH
3
*
CH
3
CHCH(CH
3
)
2
OH
*
3-Pentanol 2-Methyl-2-butanol
CH
3
CH
2
COH
CH
3
CH
3
CH
3
CH
2
CHCH
2
CH
3
OH
1-Pentanol 3-Methyl-1-butanol 2,2-Dimethyl-1-propanol
CH
3
CH
2
CH
2
CH
2
CH
2
OH (CH
3
)
3
CCH
2
OHCH
3
CHCH
2
CH
2
OH
CH
3
STEREOCHEMISTRY 163
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(c) Both stereoisomers have two equivalently substituted stereogenic centers, and so we must be
alert for the possibility of a meso stereoisomer. The structure at the left is chiral. The one at the
right has a plane of symmetry and is the achiral meso stereoisomer.
(d) The first structure is achiral; it has a plane of symmetry.
The second structure cannot be superposed on its mirror image; it is chiral.
7.25 There are four stereoisomers of 2,3-pentanediol, represented by the Fischer projections shown. All
are chiral.
There are three stereoisomers of 2,4-pentanediol. The meso form is achiral; both threo forms are
chiral.
meso-2,4-Pentanediol
CH
3
CH
3
H
H
H
OH
OH
H
CH
3
CH
3
H
H
HO
OH
H
H
CH
3
CH
3
H
H
HO
OH
H
H
Enantiomeric threo isomers
Enantiomeric erythro isomers
CH
2
CH
3
CH
3
H
HOH
OH
CH
2
CH
3
CH
3
HO
HO
H
H
Enantiomeric threo isomers
CH
2
CH
3
CH
3
HO
HOH
H
CH
2
CH
3
CH
3
HO
H
H
OH
Cl
Cl
Cl
Reference structure Mirror image Reoriented mirror image
H11013
Cl
1
4
7
Plane of symmetry passes through C-1, C-4, and C-7.
H
2
N
NH
2
CH
3
CH
3
H
H
Chiral
Plane of symmetry
NH
2
NH
2
CH
3
CH
3
H
H
Meso: achiral
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7.26 Among the atoms attached to the stereogenic center, the order of decreasing precedence is Br H11022
Cl H11022 F H11022 H. When the molecule is viewed with the hydrogen pointing away from us, the order
Br → Cl → F appears clockwise in the R enantiomer, anticlockwise in the S enantiomer.
7.27 (a)(H11002)-2-Octanol has the R configuration at C-2. The order of substituent precedence is
HO H11022 CH
2
CH
2
H11022 CH
3
H11022 H
The molecule is oriented so that the lowest ranking substituent is directed away from you and
the order of decreasing precedence is clockwise.
(b) In order of decreasing sequence rule precedence, the four substituents at the stereogenic cen-
ter of monosodium L-glutamate are
N
H11001
H
3
H11022 CO
2
H11002
H11022 CH
2
H11022 H
When the molecule is oriented so that the lowest ranking substituent (hydrogen) is directed
away from you, the other three substituents are arranged as shown.
The order of decreasing rank is counterclockwise; the absolute configuration is S.
7.28 (a) Among the isotopes of hydrogen, T has the highest mass number (3), D next (2), and H low-
est (1). Thus, the order of rank at the stereogenic center in the reactant is CH
3
H11022 T H11022 D H11022 H.
The order of rank in the product is HO H11022 CH
3
H11022 T H11022 D.
Orient with lowest ranked substituent away from you.
CH
3
TD H
3
C T
OH
C
D
H
CH
3
T
C
D
HO
T
CH
3
biological oxidation
CH
2
CH
2
CO
2
H11002
NH
3
H11001
O
2
C
H11002
Na
H11001
H
3
N
H11001
H
CH
2
CH
2
CO
2
H11002
CO
2
H11002
H
3
N
H11001
H
CH
2
CH
2
CO
2
H11002
CO
2
H11002
Cis the same as
Na
H11001
Na
H11001
OH
CH
2
CH
2
CH
3
HO H
ClCl H
F
Br
H
ClF C
Br
S-(H11001)R-(H11002)S-(H11001)R-(H11002)
C
Br
H
F
Br
Cl
C
F
H
STEREOCHEMISTRY 165
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The order of decreasing rank in the reactant is anticlockwise; the configuration is S. The order
of decreasing rank in the product is clockwise; the configuration is R.
(b) Retention of configuration means that the three-dimensional arrangement of bonds at the
stereogenic center is the same in the reactant and the product. The R and S descriptors change
because the order of precedence changes in going from reactant to product; for example, CH
3
is the highest ranked substituent in the reactant, but becomes the second-highest ranked in the
product.
7.29 Two compounds can be stereoisomers only if they have the same constitution. Thus, you should
compare first the constitution of the two structures and then their stereochemistry. The best way to
compare constitutions is to assign a systematic (IUPAC) name to each molecule. Also remember
that enantiomers are nonsuperposable mirror images, and diastereomers are stereoisomers that are
not enantiomers.
(a) The two compounds are constitutional isomers. Their IUPAC names clearly reflect this
difference.
(b) The two structures have the same constitution. Test them for superposability. To do this we
need to place them in comparable orientations.
and
The two are nonsuperposable mirror images of each other. They are enantiomers.
To check this conclusion, work out the absolute configuration of each using the Cahn–
Ingold–Prelog system.
(c) Again, place the structures in comparable orientations, and examine them for superposability.
and
is equivalent to
CH
2
CH
3
Br
CH
3
HC
H
Br
CH
2
CH
3
CH
3
is equivalent to
CH
2
CH
3
Br
CH
3
HC
CH
3
CH
3
CH
2
Br
H
(S)-2-Bromobutane
C
CH
3
CH
3
CH
2
Br
H
(R)-2-Bromobutane
C
Br
CH
3
CH
2
CH
3
H
C CH
3
CH
3
CH
2
Br
H
is equivalent to
CH
2
CH
3
H
CH
3
Br
C
CH
3
CH
3
CH
2
Br
H
CH
2
CH
3
Br
CH
3
His equivalent to
CH
3
CHCH
2
Br
OH
1-Bromo-2-propanol
CH
3
CHCH
2
OH
Br
2-Bromo-1-propanol
and
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The two structures represent the same compound, since they are superposable. (As a check,
notice that both have the S configuration.)
(d) If we reorient the first structure,
which is the enantiomer of
As a check, the first structure is seen to have the S configuration, and the second has the R con-
figuration.
(e) As drawn, the two structures are mirror images of each other; however, they represent an achi-
ral molecule. The two structures are superposable mirror images and are not stereoisomers but
identical.
( f ) The two structures—one cis, the other trans—are stereoisomers that are not mirror images;
they are diastereomers.
(g) The two structures are enantiomers, since they are nonsuperposable mirror images. Checking
their absolute configurations reveals one to be R, the other S. Both have the E configuration at
the double bond.
(h) These two structures are identical; both have the E configuration at the double bond and the R
configuration at the stereogenic center.
Alternatively, we can show their superposability by rotating the second structure 180°
about an axis passing through the doubly bonded carbons.
(i) One structure has a cis double bond, the other a trans double bond; therefore, the two are di-
astereomers. Even though one stereogenic center is R and the other is S, the two structures are
Reference structure Identical to reference structureRotate 180H11034 around this axis
OHH
HO H HO H
HO H OHH
(2R,3E)-3-Penten-2-ol (2S,3E)-3-Penten-2-ol
H
3
C
H
H
Cl
cis-1-Chloro-2-methylcyclopropane
H
3
C
HCl
H
trans-1-Chloro-2-methylcyclopropane
and are both identical
CH
2
OH
OH
CH
2
OH
H
CH
2
OH
H
CH
2
OH
HO
CH
2
CH
3
H
CH
3
Br
becomes
CH
2
CH
3
Br
CH
3
HC
CH
3
CH
3
CH
2
Br
H
STEREOCHEMISTRY 167
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not enantiomers. The mirror image of a cis (or Z) double bond is cis, and that of a trans (or E)
double bond is trans.
( j) Here it will be helpful to reorient the second structure so that it may be more readily compared
with the first.
The two compounds are enantiomers.
Examining their absolute configurations confirms the enantiomeric nature of the two
compounds.
(k) These two compounds differ in the order in which their atoms are joined together; they are
constitutional isomers.
(l) To better compare these two structures, place them both in the same format.
The two are enantiomers.
(m) Since cis-1,3-dimethylcyclopentane has a plane of symmetry, it is achiral and cannot have an
enantiomer. The two structures given in the problem are identical.
H
H
CH
3
CH
3
Plane of symmetry
OHH
HO H
CH
3
CH
2
OH
OHH
HO H
CH
3
CH
2
OH
H
3
C
CH
2
OH
H
OH
HO
H
which is equivalent to
1
2
3
45
HO
HO
1
2
3
4
5
3-Hydroxymethyl-2-cyclopenten-1-ol 3-Hydroxymethyl-3-cyclopenten-1-ol
CH
2
OH CH
2
OH
(R)-3-Hydroxymethyl-2-cyclopenten-1-ol (S)-3-Hydroxymethyl-2-cyclopenten-1-ol
S
OH
H
CH
2
OH
HO
H
CH
2
OH
R
CH
2
OH
HO
CH
2
OH
HO
CH
2
OH
HOand
which is equivalent to
Reference structure Enantiomer of
reference structure
(2R,3E)-3-Penten-2-ol (2S,3Z)-3-Penten-2-ol
HO H H OH
168 STEREOCHEMISTRY
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(n) These structures are diastereomers, that is, stereoisomers that are not mirror images. They
have the same configuration at C-3 but opposite configurations at C-2.
(o) To compare these compounds, reorient the first structure so that it may be drawn as a Fischer
projection. The first step in the reorientation consists of a 180° rotation about an axis passing
through the midpoint of the C-2@C-3 bond.
Thus
Now rotate the “back” carbon of the reoriented structure to give the necessary alignment for a
Fischer projection.
This reveals that the original two structures in the problem are equivalent.
(p) These two structures are nonsuperposable mirror images of a molecule with two nonequiva-
lent stereogenic centers; they are enantiomers.
(q) The two structures are stereoisomers that are not enantiomers; they are diastereomers.
H
3
C OH
cis-3-Methylcyclohexanol
OH
H
3
C
trans-3-Methylcyclohexanol
2S,3S2R,3R
BrH
HBr
CH
3
CO
2
H
1
2
3
4
3
2
4
1
HBr
Br H
CO
2
H
CH
3
becomes which is the same as
BrH
H Br
CO
2
H
CH
3
CO
2
H
CH
3
HBr
HBr
CH
3
CO
2
H
Br
BrH
H
is
Reference structure
BrH
H Br
CH
3
CO
2
H
BrH
HBr
CH
3
CO
2
H
X
Y
Y
X
becomes
2R,3R 2S,3R
BrH
H Br
CH
3
CO
2
H
1
2
3
4
HBr
H Br
CH
3
CO
2
H
1
2
3
4
STEREOCHEMISTRY 169
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(r) These two structures, cis- and trans-4-tert-butylcyclohexyl iodide, are diastereomers.
(s) The two structures are nonsuperposable mirror images; they are enantiomers.
(t) The two structures are identical.
(u) As represented, the two structures are mirror images of each other, but because the molecule
is achiral (it has a plane of symmetry), the two must be superposable. They represent the same
compound.
The plane of symmetry passes through C-7 and bisects the C-2@C-3 bond and the C-5@C-6
bond.
(v) The structures are stereoisomers but not enantiomers; they are diastereomers. (Both are achi-
ral and so cannot have enantiomers.)
H
3
C H
Achiral
CH
3
H
Achiral
and are stereoisomers but not mirror images
H
3
CH HCH
3
7
4
5
3
6
2
1
Reference structure
H
3
C H
7
1
2
6
3
5
4
Identical to reference
structure
is equivalent to
H
3
C
3
6
4
5
2
1
7
is equivalent to
CH
3
Reference structure Identical to reference
structure
CH
3
1
6
5
7
4
3
2
CH
3
5
6
4
3
2
1
7
is equivalent to
CH
3
Reference structure
H
3
C
2
1
6
5
4
7
3
Enantiomer of reference
structure
I
(CH
3
)
3
C
Trans
I
(CH
3
)
3
C
Cis
170 STEREOCHEMISTRY
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7.30 Write a structural formula for phytol and count the number of structural units capable of stereo-
chemical variation.
Phytol has two stereogenic centers (C-7 and C-11) and one double bond. The stereogenic centers
may be either R or S, and the double bond may be either E or Z. Eight stereoisomers are possible.
Isomer
12345678
Double bond EEEEZZZZ
Carbon-7 RSRSRSRS
Carbon-11 RSSRRSSR
7.31 (a) Muscarine has three stereogenic centers, and so eight stereoisomers have this constitution.
(b) The three substituents on the ring (at C-2, C-3, and C-5) can be thought of as being either up
(U) or down (D) in a perspective drawing. Thus the eight possibilities are:
UUU, UUD, UDU, DUU, UDD, DUD, DDU, DDD
Of these, six have one substituent trans to the other two.
(c) Muscarine is
7.32 To write a stereochemically accurate representation of ectocarpene, it is best to begin with the con-
figuration of the stereogenic center, which we are told is S.
Clearly, hydrogen is the lowest ranking substituent; among the other three substituents, two are part
of the ring and the third is the four-carbon side chain. The priority rankings of these groups are de-
termined by systematically working along the chain.
The substituents
are considered as if they were
C H11022
H
C
C
H
C
C
H
C
H
C
(Ring)
H
C
H
C
(Ring)
H
C
C
H
C
C
H
C
H
H
C
H
H H11022
(Side chain)
CHCH
2
CH CHCH
2
CH
(Ring)
CHCH
2
CH
3
CH
(Side chain)
CHCH
2
CH CHCH
2
CH
(Ring)
HCHCHCH
2
CH
3
O
H
H
H
OH
H
3
C
CH
2
N(CH
3
)
3
H11001
R
SS
HO
H11002
3,7,11,15-Tetramethyl-2-hexadecen-1-o1
HOCH
2
CH CCH
2
CH
2
CH
2
CHCH
2
CH
2
CH
2
CHCH
2
CH
2
CH
2
CHCH
3
CH
3
CH
3
CH
3
CH
3
**
STEREOCHEMISTRY 171
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Orienting the molecule with the hydrogen away from you
we place the double bonds in the ring so that the order of decreasing sequence rule precedence is
counterclockwise:
Finally, since all the double bonds are cis, the complete structure becomes:
7.33 (a) Multifidene has two stereogenic centers and three double bonds. Neither the ring double bond
nor the double bond of the vinyl substituent can give rise to stereoisomers, but the butenyl side
chain can be either E or Z. Eight (2
3
) stereoisomers are therefore possible. We can rationalize
them as
Stereoisomer C-3 C-4 Butenyl double bond
1 RRE
enantiomers
2 SS
H20903
3 RRZ
enantiomers
4 SS
H20903
5 RSE
enantiomers
6 SR
H20903
7 RSZ
enantiomers
8 SR
H20903
(b) Given the information that the alkenyl substituents are cis to each other, the number of
stereoisomers is reduced by half. Four stereoisomers are therefore possible.
(c) Knowing that the butenyl group has a Z double bond reduces the number of possibilities by
half. Two stereoisomers are possible.
(d) The two stereoisomers are
and
CH CHCH
2
CH
3
CH CH
2
1
2
3
45
H
HH
H CH CHCH
2
CH
3
Lowest
Second highest
Third highestHighest priority
H CH CHCH
2
CH
3
172 STEREOCHEMISTRY
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(e) These two stereoisomers are enantiomers. They are nonsuperposable mirror images.
7.34 In a substance with more than one stereogenic center, each center is independently specified as R
or S. Streptimidone has two stereogenic centers and two double bonds. Only the internal double
bond is capable of stereoisomerism.
The three stereochemical variables give rise to eight (2
3
) stereoisomers, of which one is streptimi-
done and a second is the enantiomer of streptimidone. The remaining six stereoisomers are dia-
stereomers of streptimidone.
7.35 (a) The first step is to set out the constitution of menthol, which we are told is 2-isopropyl-
5-methylcyclohexanol.
Since the configuration at C-1 is R in (H11002)-menthol, the hydroxyl group must be “up” in our
drawing.
Because menthol is the most stable stereoisomer of this constitution, all three of its sub-
stituents must be equatorial. We therefore draw the chair form of the preceding structure,
which has the hydroxyl group equatorial and up, placing isopropyl and methyl groups so as to
preserve the R configuration at C-1.
(CH
3
)
2
CH
HO
H
CH
3
1 5
2
(H11002)-Menthol
CH(CH
3
)
2
CH
3
OH
H
R configuration at C-1
5
2
1
CH(CH
3
)
2
CH
3
OH
5
1
2
2-Isopropyl-5-methylcyclohexanol
H
H
H
3
C
CH
3
H
H
H NH
OH
O
O
O
E
S
R
Mirror plane
STEREOCHEMISTRY 173
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(b) To transform the structure of (H11002)-menthol to that of (H11001)-isomenthol, the configuration at C-5
must remain the same, whereas those at C-1 and C-2 are inverted.
(H11001)-Isomenthol is represented here in its correct configuration, but the conformation with two
axial substituents is not the most stable one. The ring-flipped form will be the preferred con-
formation of (H11001)-isomenthol:
7.36 Since the only information available about the compound is its optical activity, examine the two
structures for chirality, recalling that only chiral substances can be optically active.
The structure with the six-membered ring has a plane of symmetry passing through C-1 and C-4.
It is achiral and cannot be optically active.
The open-chain structure has neither a plane of symmetry nor a center of symmetry; it is not super-
posable on its mirror image and so is chiral. It can be optically active and is more likely to be the
correct choice.
7.37 Compound B has a center of symmetry, is achiral, and thus cannot be optically active.
The diol in the problem is optically active, and so it must be chiral. Compound A is the naturally oc-
curring diol.
7.38 (a) The equation that relates specific rotation [H9251]
D
to observed rotation H9251 is
[H9251]
D
H11005
100H9251
H5007
cl
Compound B: not optically active
(center of symmetry is midpoint of C-16 C-17 bond)
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
HO
OH
16
17
CH
3
CH
3
Achiral; [H9251]
d
0H11034 Chiral; can be optically active
H
HO H
OH
HOH
HOH
CH
2
OH
CH
2
OH
OH
HO
HO OH
CO
2
H
1
2
34
5
6
OH
CH
3
(CH
3
)
2
CH
OH
(CH
3
)
2
CH
CH
3
Most stable conformation of
(H11001)-isomenthol
(CH
3
)
2
CH
HO CH
3
1 5
2
(H11002)-Menthol (H11001)-Isomenthol
(CH
3
)
2
CH
OH
CH
3
1
5
2
174 STEREOCHEMISTRY
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where c is concentration in grams per 100 mL and l is path length in decimeters.
[H9251]
D
H11005
H11005H11002130o
(b) The optical purity of the resulting solution is 10/15, or 66.7%, since 10 g of optically pure
fructose has been mixed with 5 g of racemic fructose. The specific rotation will therefore be
two thirds (10/15) of the specific rotation of optically pure fructose:
[H9251]
D
H11005
H5007
2
3
H5007
(H11002130o) H11005H1100287o
7.39 (a) The reaction of 1-butene with hydrogen iodide is one of electrophilic addition. It follows
Markovnikov’s rule and yields a racemic mixture of (R)- and (S)-2-iodobutane.
(b) Bromine adds anti to carbon–carbon double bonds to give vicinal dibromides.
The two stereoisomers are enantiomers and are formed in equal amounts.
(c) Two enantiomers are formed in equal amounts in this reaction, involving electrophilic addi-
tion of bromine to (Z)-2-pentene. These two are diastereomeric with those formed in part (b).
(d) Epoxidation of 1-butene yields a racemic epoxide mixture.
(e) Two enantiomeric epoxides are formed in equal amounts on epoxidation of (Z)-2-pentene.
peroxyacetic acid
CH
2
Cl
2
H11001
(2S,3R)-2,3-Epoxypentane
H
3
C CH
2
CH
3
HH
(Z)-2-Pentene
H
3
C CH
2
CH
3
O
H H
(2R,3S)-2,3-Epoxypentane
H
3
C CH
2
CH
3
O
HH
CH
3
CH
2
CH CH
2
peroxyacetic acid
CH
2
Cl
2
(S)-1,2-Epoxybutane (R)-1,2-Epoxybutane
H11001CH
3
CH
2
O
H
CH
3
CH
2
O
H
CH
2
CH
3
H
3
C
H H
(Z)-2-Pentene (2R,3R)-2,3-Dibromopentane (2S,3S)-2,3-Dibromopentane
Br
2
CCl
4
H11001
Br
Br
H
H
CH
3
CH
2
CH
3
CH
3
CH
2
Br
Br
H
HCH
3
CH
2
CH
3
H
3
C
H
H
(E)-2-Pentene
Br
Br
H
H
CH
2
CH
3
H
3
C
(2R,3S)-2,3-Dibromopentane
Br
Br
CH
3
H
H
CH
2
CH
3
(2S,3R)-2,3-Dibromopentane
Br
2
CCl
4
H11001
CH
3
CH
2
CH CH
2
HI
I
H
3
C
CH
3
CH
2
C H11001 I
H
CH
3
CH
2
CH
3
C
1-Butene (R)-2-Iodobutane (S)-2-Iodobutane
H
100(H110025.20o)
H5007H5007H5007
(2.0 gH20862100 mL)(2 dm)
STEREOCHEMISTRY 175
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The reaction is a stereospecific syn addition. The cis alkyl groups in the starting alkene remain
cis in the product epoxide.
( f ) The starting material is achiral, so even though a chiral product is formed, it is a racemic mix-
ture of enantiomers and is optically inactive.
(g) Recall that hydroboration–oxidation leads to anti-Markovnikov hydration of the double
bond.
The product has two stereogenic centers. It is formed as a racemic mixture of enantiomers.
7.40 Hydration of the double bond of aconitic acid (shown in the center) can occur in two regiochemi-
cally distinct ways:
One of the hydration products lacks a stereogenic center. It must be citric acid, the achiral, optically
inactive isomer. The other one has two different stereogenic centers and must be isocitric acid, the
optically active isomer.
7.41 (a) Structures A and B are chiral. Structure C has a plane of symmetry and is an achiral meso
form.
(b) Ozonolysis of the starting material proceeds with the stereochemistry shown. Compound B is
the product of the reaction.
(c) If the methyl groups were cis to each other in the cycloalkene, they would be on the same side
of the Fischer projection in the product. Compound C would be formed.
7.42 (a) The E2 transition state requires that the bromine and the hydrogen that is lost be antiperipla-
nar to each other. Examination of the compound given in the problem reveals that loss of
HH
HH
HCH
3
H
3
CH
CH O
CH O
H
3
C
H
3
C
H
3
C
H
3
C
H
H
CH O
CH O
1. O
3
2. Zn, H
2
O
which is equivalent to
Compound B
HO
2
CCH
2
CHCHCO
2
H
CO
2
H
*
*
OH
Chiral
(isocitric acid)
HO
2
CCH
2
CCH
2
CO
2
H
CO
2
H
OH
Achiral
(citric acid)
Aconitic acid
C
H
CO
2
H
HO
2
C
HO
2
CCH
2
C
H
2
O H
2
O
CH
3
1,5,5-Trimethylcyclopentene
HO
H
3
C H
H
H
CH
3
H
HO
(1S,2S)-2,3,3-Trimethylcyclopentanol
(1R,2R)-2,3,3-Trimethylcyclopentanol
1. B
2
H
6
2. H
2
O
2
, HO
H11002
H11001
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
1,5,5-Trimethylcyclopentene
H
3
C H
(R)-1,1,2-Trimethylcyclopentane
CH
3
H
(S)-1,1,2-Trimethylcyclopentane
H
2
Pt
H11001
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
176 STEREOCHEMISTRY
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bromine and the deuterium will yield trans-2-butene, whereas loss of the bromine and the hy-
drogen on C-3 will yield cis-2-butene.
The trans-2-butene that forms does not contain deuterium, but cis-2-butene does. 1-Butene
also contains deuterium.
(b) The starting material in part (a) is the erythro isomer. The relative positions of the H and C at
C-3 are reversed in the threo isomer. The erythro and threo isomers can be drawn using
Fischer projections:
Because the positions of the H and D on C-3 in the threo isomer are opposite that in the
erythro, the deuterium content of cis- and trans-2-butene would be reversed. trans-2-Butene
obtained from the threo isomer would contain deuterium, and cis-2-butene would not. 1-
Butene obtained from the threo isomer would also contain deuterium.
7.43 Bromine adds to the unknown compound, suggesting the presence of a double bond in addition to
the five-membered ring. The following are possible structures for the unknown:
CH
3
1-Methylcyclopentene
CH
3
3-Methylcyclopentene
CH
3
4-MethylcyclopenteneMethylenecyclopentane
CH
2
CH
3
H
H
CH
3
Br
D
H
H
Br
D
Erythro
CH
3
CH
3
Threo
CH
3
CHCHCH
3
D
Br
E2
CHCHCH
3
D
CH
2
1-Butene
CC
H
H
D
Br
CH
3
CH
3
CC
H
H
D
Br
CH
3
CH
3rotation around
C-2 - C-3 bond
E2 (-DBr) E2 (-HBr)
CC
H
3
C
H
H
CH
3
trans-2-Butene
CC
H
3
C
H
CH
3
D
cis-2-Butene
can be redrawn as
C
C
H
Br
H
3
C
CH
3
H
D
STEREOCHEMISTRY 177
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Which of these form diastereomeric dibromides on anti addition of bromine?
We are told in the problem that two diastereomeric bromides were formed, thus the compound
must be 3-methylcyclopentene.
7.44 Dehydration of this tertiary alcohol can yield 2,3-dimethyl-1-pentene or 2,3-dimethyl-2-pentene.
Only the terminal alkene in this case is chiral.
The 2,3-dimethyl-1-pentene formed in the dehydration reaction must be optically pure because it
arises from optically pure alcohol by a reaction that does not involve any of the bonds to the stereo-
genic center. When optically pure 2,3-dimethyl-1-pentene is hydrogenated, it must yield optically
pure 2,3-dimethylpentane—again, no bonds to the stereogenic center are involved in this step.
CH
3
CH
2
CHC(CH
3
)
2
H
3
C OH
2,3-Dimethyl-2-pentanol
(chiral, optically pure)
2,3-Dimethyl-1-pentene
(chiral, optically pure)
*
CH
3
CH
2
CHC
CH
3
*
CH
2
CH
3
2,3-Dimethylpentane
(chiral, optically pure)
CH
3
CH
2
CHCH(CH
3
)
2
CH
3
*
2,3-Dimethyl-2-pentene
(achiral, optically inactive)
H11001 CH
3
CH
2
C
CH
3
CH
3
CH
3
C
H
2
, Pt
2,3-Dimethylpentane
(chiral, optically inactive)
CH
3
CH
2
CHCH(CH
3
)
2
CH
3
*
H
2
, Pt
CH
3
H
Br BrBrBr
CH
3
H CH
3
H
Br
2
4-Methylcyclopentene
H11001
(enantiomers)
CH
3
H
Br
Br
CH
3
H CH
3
H
Br
Br
Br
2
3-Methylcyclopentene
H11001
(diastereomers)
CH
3
CH
3
Br
Br
Br
Br
2
1-Methylcyclopentene
H11001
(enantiomers)
CH
3
Br
CH
2
BrBr
Methylenecyclopentane
CH
2
Br
2
(only product)
178 STEREOCHEMISTRY
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The 2,3-dimethyl-2-pentene formed in the dehydration reaction is achiral and must yield racemic
2,3-dimethylpentane on hydrogenation.
Because the alkane is 50% optically pure, the alkene fraction must have contained equal amounts
of optically pure 2,3-dimethyl-1-pentene and its achiral isomer 2,3-dimethyl-2-pentene.
7.45 (a) Oxygen may be transferred to either the front face or the back face of the double bond when
(R)-3-buten-2-ol reacts with a peroxy acid. The structure of the minor stereoisomer was given
in the problem. The major stereoisomer results from addition to the opposite face of the dou-
ble bond.
(b) The two epoxides have the same configuration (R) at the secondary alcohol carbon, but oppo-
site configurations at the stereogenic center of the epoxide ring. They are diastereomers.
(c) In addition to the two diastereomeric epoxides whose structures are shown in the solution to
part (a), the enantiomers of each will be formed when racemic 3-buten-2-ol is epoxidized. The
relative amounts of the four products will be:
7.46–7.49 Solutions to molecular modeling exercises are not provided in this Study Guide and Solutions Man-
ual. You should use Learning By Modeling for these exercises.
SELF-TEST
PART A
A-1. For each of the following pairs of drawings, identify the molecules as chiral or achiral and
tell whether each pair represents molecules that are enantiomers, diastereomers, or identical.
(a)
(b)
and
H
H
H
Cl
CH
3
H
3
C
H
H
H CH
3
CH
3
Cl
3 4
C
Cl
CH
3
CH
2
C
CH
3
CH
3
Cl
CH
2
CH
3
and
CH
3
CH
3
1 2
30%
H OH
O
CH
2
O
CH
2
30%
HO H
Enantiomeric forms of
major stereoisomer,
totaling 60%
H
H
3
C
H
H
3
C
H OH
CH
2
O
20%
HO
H
CH
2
O
20%
Enantiomeric forms of
minor stereoisomer,
totaling 40%
H
H
3
C
H
H
3
C
H
CH
2
H
OH
H
3
C
H
H
3
C
H
H
3
C
CH
2
O
O
CH
2
peroxy acid
H11001
(R)-3-Buten-2-ol Minor stereoisomer Major stereoisomer
H OH H OH
STEREOCHEMISTRY 179
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(c)
(d)
(e)
A-2. Specify the configuration of each stereogenic carbon in the preceding problem, using the
Cahn–Ingold–Prelog R–S system.
A-3. Predict the number of stereoisomers possible for each of the following constitutions. For
which of these will meso forms be possible?
A-4. Using the skeletons provided as a guide,
(a) Draw a perspective view of (2R,3R)-3-chloro-2-butanol.
(b) Draw a sawhorse diagram of (R)-2-bromobutane.
(c) Draw Fischer projections of both these compounds.
A-5. Draw Fischer projections of each stereoisomer of 2,3-dichlorobutane. Identify each stereo-
genic center as R or S. Which stereoisomers are chiral? Which are not? Why?
A-6. (a) The specific rotation of pure (H11002)-cholesterol is H1100239o. What is the specific rotation of a
sample of cholesterol containing 10% (H11001)-cholesterol and 90% (H11002)-cholesterol.
(b) If the rotation of optically pure (R)-2-octanol is H1100210o, what is the percentage of the
S enantiomer in a sample of 2-octanol that has a rotation of H110024o?
HH
CH
3
H
3
C
C
CH
3
C
CH
3
CH
3
Cl Cl
(a)
CH
3
CHCHCHCH
3
(b)
Br Br Cl
CH
2
CHCH
3
CHCHCH(c)
OH
Cl H
9 10
H Cl
CH
3
Br
Br
H
H
CH
2
CH
3
CH
3
Br
Br
H
H
CH
2
CH
3
and
87
OH
OH
HO
HO
and
5 6
180 STEREOCHEMISTRY
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A-7. Write the organic product(s) expected from each of the following reactions. Show each
stereoisomer if more than one forms.
(a) 1,5,5-Trimethylcyclopentene and hydrogen bromide
(b)(E)-2-Butene and chlorine (Cl
2
)
(c)(Z)-2-Pentene and peroxyacetic acid
A-8. Give the IUPAC name, including stereochemistry, for the following:
A-9. How many stereoisomeric products are obtained from the reaction of (S)-3-chloro-1-butene
with hydrogen bromide? What is their relationship (enantiomers, diastereomers)?
A-10. Write the final product of the following reaction sequence, clearly showing its stereochem-
istry. Is the product achiral, a meso compound, optically active, or a racemic mixture?
PART B
B-1. The structure of (S)-2-fluorobutane is best represented by
B-2. Which one of the following is chiral?
(a) 1,1-Dibromo-1-chloropropane
(b) 1,1-Dibromo-3-chloropropane
(c) 1,3-Dibromo-1-chloropropane
(d) 1,3-Dibromo-2-chloropropane
B-3. Which of the following compounds are meso forms?
(a) 1 only (c) 1 and 2
(b) 3 only (d) 2 and 3
123
CH
3
CH
3
CH
2
CH
3
OH
OH
CH
3
H
H
CH
3
Cl
H
CH
3
H
Cl
(a)(c)
(d)
CH
3
CHCH
2
CH
3
F
CF
H
3
C
CH
2
CH
3
H
(b) CH
H
3
C
CH
2
CH
3
F
H
CH
2
CH
3
CH
3
F
OH
H
2
SO
4
, heat 1. B
2
H
6
2. H
2
O
2
, HO
H11002
OH
CH
2
CH
3
CH
3
Cl CH
2
Br
H
H
Br
(a)(b)
STEREOCHEMISTRY 181
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B-4. The 2,3-dichloropentane whose structure is shown is
(a)2R,3R (b)2R,3S (c)2S,3R (d)2S,3S
B-5. The separation of a racemic mixture into the pure enantiomers is termed
(a) Racemization (c) Isomerization
(b) Resolution (d) Equilibration
B-6. Order the following groups in order of R–S ranking (4 is highest):
4321
(a)CBDA
(b)ADBC
(c)CDAB
(d)C BA
B-7. A meso compound
(a) Is an achiral molecule that contains stereogenic centers.
(b) Contains a plane of symmetry or a center of symmetry.
(c) Is optically inactive.
(d) Is characterized by all of these.
B-8. The S enantiomer of ibuprofen is responsible for its pain-relieving properties. Which one of
the structures shown is (S)-ibuprofen?
B-9. Which one of the following is a diastereomer of (R)-4-bromo-cis-2-hexene?
(a)(S)-4-bromo-cis-2-hexene (d)(S)-5-bromo-trans-2-hexene
(b)(R)-4-bromo-trans-2-hexene (e)(R)-5-bromo-trans-2-hexene
(c)(R)-5-bromo-cis-2-hexene
C
C
C
CH
3
C HOH
O
C
C
O
OH
C
C
O
OH
H
OH
O
(a)
(b)
(c)
(d)
CH
3
H
H
H
3
C
H
3
C
CH(CH
3
)
2
C(CH
3
)
3
CH
2
CH
2
Br CH
2
Br
ABCD
CH
2
CH
3
Cl
H
CH
3
H
Cl
182 STEREOCHEMISTRY
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B-10. The reaction sequence
will yield:
(a) A pair of products that are enantiomers
(b) A single product that is optically active
(c) A pair of products that are diastereomers
(d) A pair of products one of which is meso
B-11. Which of the following depict the same stereoisomer?
(a) 1 and 2 (b) 1 and 3 (c) 2 and 3 (d) 1, 2, and 3
B-12. A naturally occurring substance has the constitution shown. How many stereoisomers may
have this constitution?
(a)2 (b)8 (c)16 (d)64 (e) 128
B-13. Acid-catalyzed hydration of an unknown compound X, C
6
H
12
, yielded as the major product a
racemic mixture Y, C
6
H
14
O. Which (if any) of the following is (are) likely candidate(s) for X?
(a) 3 only (c) 1 and 3 (e) None of these
(b) 2 only (d) 2 and 3
B-14. The major product(s) from the reaction of Br
2
with (Z)-3-hexene is (are)
(a) Optically pure
(b) A racemic mixture of enantiomers
(c) The meso form
(d) Both the racemic mixture and the meso form
231
O
CH
2
OHHO
HO CH CHCH CHCH
2
CH
2
CH
3
C
CH
2
CH
3
ClBr
CH
3
1
C
CH
2
CH
3
BrCH
3
Cl
3
C
CH
3
ClCH
3
CH
2
Br
2
CCHCH
2
H
3
C
CH
2
CH
3
H
CH
3
COOH
O
STEREOCHEMISTRY 183
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