Chapter 9

9.1 Which of the following objects are chiral?

(a) A screwdriver (b) A screw (c) A bean stalk (d) A shoe (e) A hammer
Solution: chiral objects: screw, bean stalk, shoe.

9.2 Identify the chirality centers in the following molecules. Build molecular models if you need
help.
(a) (b) (c)
H3CO

H CH3

CH2CH2CH3 HO
N CH3
N H
H H
H H

Coniine menthol Dextromethorphan

(poison hemlock) (flavoring agent) (cough suppressant)

Solution:

chirality center

CH2CH2CH3

N
H
(a),

H CH3
chirality center(R)
HO

chirality center(R) H H chirality center(S)

(b),

H3CO

chirality center(S)

R
N CH3
H
H

chirality center(S)
(c),
9.3 Alanine, an amino acid found in proteins, is chiral. Draw the two enantiomers of alanine using
the standard conversion of solid, wedged, and dashed lines.
NH2
CH3CHCO 2H Alanine

Solution:

H H

CO2H HO2C
H2N NH2
CH3 H3C

S R

9.4 Identify the chirality centers in the following molecules.

(a)
HO H
H
C
HO C O
C C
H2
S H OH
(b)
R

H H2 F2
C C
C O H

F Cl

9.5 A 1.50g sample of coiine, the toxic extract of poison hemlock,was dissolved in 10.0mL of ethanol
and placed in a sample cell with a 5.00 cm pathlength. The observed rotation at the sodium D line was
+1.21°. Calculate [α] D for coiine.
Solution:
Sample concentration: 1.50g/10.0mL=0.150g/mL
[α] D=+1.21°/(0.150 g/mL *5.00*0.1dm)=16.1°

9.6 Assign priorities to the following sets of substituents:

(a) ­H, ­Br, ­CH2CH3, ­CH2CH2OH
Solution:
­Br > ­CH2CH2OH > ­CH2CH3 > ­H

(b) ­CO2H, ­CO2CH3, ­CH2OH, ­OH

Solution:
­OH > ­CO2CH3 > ­CO2H > ­CH2OH
(c) ­CN, ­CH2NH2, ­CH2NHCH3, ­NH2
Solution:
­NH2 > ­CN > ­CH2NHCH3 > ­CH2NH2

(d) ­Br, ­CH2Br, ­Cl, ­CH2Cl

Solution:
­Br> ­Cl > ­CH2Br > ­CH2Cl

9.7 Orient each of the following drawings so that the lowest-priority group is toward the rear, and
the assign R or S configuration:
1 3 4

4 3 2 4 1 2
2 1 3
Solution:
1 3 4

4 3 2 4 1 2
2 1 3

4 4 4
1 3
2 3 3 2

2 1 1

S R S
9.8 Assign R or S configuration to the chirality center in each of the following molecules:
(a) CH3 (b) OH (c)
NH2
H CH3
C C

H COOH H3C COOH CN

Br H
Solution:
 3 1 1
(a) CH3 (b) OH (c)
NH2
H CH3 3
C C 4
3 2
4 H Br COOH H3C
H
COOH CN
1 2 2
4
S S R
9.9 Draw a tetrahedral representation of (S)-2-pentanol (2-hydroxypentane).
Solution:
H

HO

9.10 Assign R or S configuration to the chirality center in the following molecular model of the
amino acid methionine(red=O, blue=N, yellow=S)

Solution:
First you can change the molecular model into the corresponding line-bond structure
following, and then assign R or S after identifying the priority of the atoms attaching to the
chirality center:

3
2
O
H2
S C H
H3C C C O
H2
H2N H S

1
9.11 Assign R or S configuration to the chirality center in the following molecules. Which are
enantiomers, and which are diastereomers?

Br CH3 CH3 H
H CH3 H Br Br H Br CH3
C C C C

C C C C
H OH H3C H H CH3 H3C OH
CH3 OH OH H

(a) (b) (c) (d)

Solution:
First you can identify the priority of the group attached to the chirality center as following

Br 〉—OH 〉—CH3 〉H
And then you can assign R or S easily:

R S R S

Br CH3 CH3 H
H CH3 H Br Br H Br CH3
C C C C

C C C C
H OH H3C H H CH3 H3C OH
CH3 OH OH H

R
R S S
(a) (b) (c) (d)
Obviously (a) and (d), (b) and (c) are enantiomers for their mirror relationships, however, (a) and
(d) are diastereomeric with (b) and (c).

9.12 Chloramphenicol, a powerful antibiotic isolated in 1949 form the Streptomyces venezuelae
bacterium, is active against a broad spectrum of bacterial infections and is particularly valuable
against typhoid fever. Assign R,S configurations to the chirality centers in chloramphenicol
 H OH
H2
C OH

Cl
H HN C CH
Cl
O2N
O
Solution:

1
R H OH
H2 3
2 C OH
3 R
Cl
H HN C CH
Cl
O2N 1
O

9.13 Assign R, S configuration to each chirality center in the following molecular model of the
amino acid isoleucine (red = O, blue = N):
Solution
S

S
9.14
Which of the following structures represent meso compounds?
OH OH CH3 H
(a) H (b) H (c) (d)
Br CH3
OH OH C
H
H H C
H3 C H

Br

Solution: (a) (d)

9.15
Which of the following have a meso form?
(a) 2,3-Dibromobutane (b) 2,3-Dibromopentane (c) 2,4-Dibromopentane
Solution: (a) (c)

9.16
Does the following structure represent a meso compound? If so, indicate the symmetry
plane(red=O).

Solution: It is a meso compound. The symmetry plane is shown as following :

OH

9.17
How many chirality centers does morphine have? How many stereoisomers of morphine are
possible in principle?
CH3
N

* H
*
*
* *

HO O OH
H H morphine
There are five chirality centers in morphine .It has 25 stereoisomers in principle.

9.18
What stereoisomers would result from reaction of ( )-lactic acid with
(S)-1-phenyl-ethylamine,and what is the relationship between them?
Solution:
The products of the reaction of ( )-lactic acid with (S)-1-phenyl-ethylamine is a R,S salt
and a S,S salt. They are diastereomers.

9.19
What kinds of isomers are the following pairs?
(a) (S)-5-Chloro-2-hexene and chlorocyclohexane
(b) (2R,3R)-Dibromopentane and (2S,3R)-dibromopentane
Solution:
(a)

Cl
Cl
H
They are constitutional isomers.
(b)
 H Br
Br H
R s
R R
H H
Br Br
They are diastereomers.

9.20
Addition of Br2 to an unsymmetrical alkene such as cis-2-hexene leads to racemic
2,3-dibromohexane, even though reaction of Br- ion with the unsymmetrical bromonium
intermediate is not equally likely at both ends. Make drawings of the intermediate and the
products, and explain the observed stereochemical result.
Solution:

cis-2-hexene
There are two intermediates leads to two products respectively.

Br
Br
R S
H
H R
Br
H S
H Br
H major
H Br

Br
Br
S Br
R
H
H S
H R
H Br
H Br H major

The result is that there are racemic mixture of (2S,3S) and (2R,3R) 2,3-dibromoheane.

9.21
Predict the stereochemistry outcome of the reaction of Br2 with trans-2-hexene, and explain your
reasoning.
Solution:

There are two intermediates lead to two products respectively.

 H H
Br Br
S
R Br R H
Br H
S
H H major
Br
H
Br H H
S Br
R
R
S Br
Br major H
H Br H
The outcome is that racemic mixture of (2S,3R) and (2R,3S).
The reason is that: the first step can occur equally well from either face of the double bond,
to give a 50:50 mixture of enantiomeric bromonium ions. Because the bromonium ions do
not have symmetry planes, reaction on the left and right is not equally likely, so an unequal
mix of (2S,3R) or (2R,3S) and (2R,3S) or (2S,3R) will be formed from each. The minor
product from one bromonium ion, however, will be the major product from the other, so
overall a 50:50(racemic)mixture of (2S,3R) and (2R,3S) dibromides will result.

9.22:
What products are formed from reaction of HBr with racemic (+)-4-methyl-hexene? What can you say
about the relative amounts of the products? Is the product mixture optically active?
Solution: Racemic mixture (1R,3S),(1S,3S) and (1S,3R),(1R,3R)
Ratio 50:50
Optically inactive
9.23:
What products are formed from reaction of HBr with 4-methyl-cyclopentene? What can you say about
the relative amounts of the products?
Solution: Racemic mixture (1R,3R),(1S,3R) and (1S,3R),(1S,3S)
Ratio not 50:50
9.24:
Identify the indicated hydrogens in the following molecules as pro-R or pro-S.
Solution:
pro-R pro-S
pro-S pro-R

H H H
H

CHO CO2
HO H3C

(a) HO H (b) H3N H

9.25
Identify the indicated faces in the following molecules as re or si:
 re face

C
H3C
CH2OH

(a) Solution: si face

re face

C CH2OH
H3C C

H si face
(b) Solution:

9.26
Lactic acid buildup in tired muscles results from reduction of pyruvate. If the reaction occurs from the
re face, what is the stereochemistry of the product？
O OH

C CH
H3C CO2 H3 C CO2
OH

CO2
H3C
Solution: It’s H and is S-Lactate.

9.27
Which of the following structures are identical?
(a)
It’s R configuration.

(b)
It’s R configuration.
(c)
It’s S configuration.

(d)

It’s R configuration.
Solution: (a)(b)(d) are identical.

9.28:
Assign R or S configuration to the chirality centers in the following molecules(red=O, blue=N):

(a) Serine (b)

 Adrenaline

H OH
N OH
H H
C (S) HO N
H
(R)
H H
OH
H HO

Solution: (a) Serine (b) Adrenaline

9.29:
Witch, if any, of the following structures represent meso compounds?(red=O. blue=N,
yellow-green=Cl.)

(a) (b)

(c)
HO OH

(R)
H
Solution: (a) (S) H There are two chirality centers which are of
different direction, and there is a symmetrical plane, so it is a meso-compound.
H2 N H H2N H

(b) (R) (S) Just the same as problem (a), there are two chirality centers which are
of different direction, and there is a symmetrical plane, so it is a meso compound.
Cl H

(R) (R)
(c) Cl H As there are two chirality centers with the same direction, it is not a meso
compound.

9.30:
Assign R or S configuration to each chirality center in paeudophedrine, an over-the-counter
decongestant found in cold remedies(red=O, blue=N).

Solution:

HO H
H
(R) N
(S)

9.31
Polarimeters for measuring optical rotation are so sensitive that they can measure rotations to 0.0010, an
important fact when only small amounts of sample are available. Ecdysone, for example, is an insect
hormone that controls molting in the silkworm moth. When 7.00 mg ecdysone was dissolved in 1.00 ml
chloroform and the solution was placed in a cell with a 2.00 cm pathlength, an observed rotation of
+0.0870 was found. Calculate [α]D for ecdysone.
Solution: C=7.00mg/1.00ml=0.007g/ml
[α]D=α/(l*C)= +0.0870/(2.00cm*0.007g/ml)=+62.140

9.32
Which of the following compounds are chiral? Draw them, and label the chirality centers.
(a) 2,4-Dimethylheptane (b) 5-Ethyl-3,3-dimethylheptane
(c) cis-1,4-Dichlorocyclohexane (d) 4,5-Dimethyl-2,6-octadiyne
Solution: (a) 2,4-Dimethylheptane and (d) 4,5-Dimethyl-2,6-octadiyne are chiral. Followings are
their structures.
CH3
∗

(a) CH3
CH3

∗
∗

H
(d) H CH3

9.33
Draw chiral molecules that meet the following descriptions:
(a) A chloroalkane, C5H11Cl (b) An alcohol, C6H14O
(c) An alkene, C6H12 (d) An alkane, C8H18
H2 H2
H3C CH C C CH3

Solution: (a) Cl
H H2 H2 H2
H3C C C C C CH3

(b) OH

(c)
H H2
H2C C C C CH3
H
CH3
(d)
CH3

9.34
Eight alcohols have the formula C5H12O. Draw them. Which are chiral?
Solution:
Not chiral:

OH
OH
OH OH
OH
Chiral:
OH

* * OH *
OH
9.35
Draw the nine chiral molecules that have the formula C6H13Br
Solution:
Br Br Br

* * * * * *
Br Br
CH2Br
Br
* * * Br *
Br
9.36
Draw compounds that fit the following descriptions:
(a) A chiral alcohol with four carbons.
(b) A chiral carboxylic acid with the formula C5H10O2
(c) A compound with two chirality centers
(d) A chiral aldehyde with the formula C3H5BrO
OH
C
H CH C CH
Solution: (a) 3 2 H 3
COOH
C
H CH C H
(b) 3 2 CH3

COOH
H OH
HO H
(c) COOH
CHO
C H
(d) H3C Br
9.37
Draw examples of the following:
(a) A basketball (b) A fork (c) A wine glass
(d) A golf club (e) A monkey wrench (f) A snowflake
Solution: (e) A monkey wrench is chiral.

9.38
Penicillin V is an important broad-spectrum antibiotic that contains three chirality centers. Identify
them:
 H
H H
N
S
O C CH3
* * Penicillin V
O N CH3
*
O
H
Solution: CO2 H

9.39
Draw examples of the following:
(a) A meso compound with the formula C8H18
CH2CH3
H CH3
C

C
H CH3
Solution: CH2CH3

(b) A meso compound with the formula C9H20

H H

C C
H3CH2C CH2 CH2CH3
Solution: H3C CH3

(c) A compound with two chirality centers, one R and the other S
CH3
H Br
C

C
H3C H
Solution: OH

9.40
What is the relationship between the specific rotations of (2R,3R)-dichloropentane and
(2S,3S)-dichloropentane? Between (2R,3S)-dichloropentane and (2R,3R)-dichloropentane?
Solution: (2R,3R)-dichloropentane and (2S,3S)-dichloropentane are enantiomers.
(2R,3S)-dichloropentane and (2R,3R)-dichloropentane are diastereomers.
Cl Cl Cl

(R) (R) (R) (S) (S) (S)

Cl Cl Cl

(2R,3R)-dichloropentane (2R,3S)-dichloropentane (2S,3S)-dichloropentane

9.41
What is the stereochemical configuration of the enantiomer of (2S,4R)-dibromooctane?
Solution: (2R,4S)-dibromooctane is the stereochemical configuration of the enantiomer of
(2S,4R)-dibromooctane.
Br Br Br Br

(S) (R) (R) (S)

(2R,4S)-dibromooctane (2S,4R)-dibromooctane

9.42
What are the stereochemical configurations of the two diastereomers of (2S,4R)-dibromooctane?
Solution: (2S,4S)-dibromooctane and (2R,4R)-dibromooctane are the stereochemical
configurations of the two diastereomers of (2S,4R)-dibromooctane.
Br Br Br Br

(S) (S) (R) (R)

(2S,4S)-dibromooctane (2R,4R)-dibromooctane

Br Br

(R) (S)

(2S,4R)-dibromooctane

9.43
Orient each of the following drawings so that the lowest-priority group is toward the rear , and then
assign R or S configuration:

G4 G3 G4

G1 G3 G4 G1 G3 G2
(a). G2 (b). G2 (c). G1
Solution
 G4 G4 G4
G1 G2 G2 G3 G3 G1

(a). G3 R (b). G1 R (c).

G2 R

9.44
Assign Cahn-Ingold-Prelog priorities to the following sets of substituents:
C CH2 CH(CH3)2 C(CH3)3 CH2CH3
(a). H

C CH C CH2 C(CH3)3
H
(b).

CO2CH3 COCH3 CH2OCH3 CH2CH3

(c).

(d). C N CH2Br CH2CH2Br Br

Solution:
C(CH3)3 > C CH2 > CH(CH3)2 > CH2CH3
(a). H
(b).

> C CH > C(CH3)3 > C CH2

H

(c).
CO2CH3 > COCH3 > CH2OCH3 > CH2CH3

(d). Br > CH 2Br > C N > CH 2CH 2 Br

9.45
Assign R or S configuration to the chirality centers in the following molecules
Cl H

H OCH3
H OH

(a). (b). (c). HOH2C CO2H

Solution:
 Cl H

H OH S H OCH3

(a). S (b). (c). HOH2C

S CO2H

9.46
Assign R or S configuration to each chirality center in the following molecules:
(a)
OH
H
S

S
Cl
H
(b)
S S
H CH3
H3C
C H
H2

(c)
R S
HO OH

H3C CH3

9.47
Assign R or S configuration to each chirality center in the following biological molecules:
(a)
 Biotin

H H
N N S

H H

R S
CH2CH2CH2CH2 CO2

S
(b)

Prostaglandin E1

O R
H
CO2H

S
R
S

HO H
H HO H

9.48
Draw tetrahedral representations of the following molecules:
(a) (S)-2-Butanol, CH3CH2CH(OH)CH3
OH

C
H3C CH2CH3
H
(b) (R)-3-Chloro-1-pentene
Cl

H2 C C
CH2CH3
C
H H

9.49
Draw tetrahedral representations of the two enantiomers of the amine acid cysteine,
HSCH2CH(NH2)COOH, and identify each as R or S.
Solution:
 H H

C C
COOH HOOC
HSH2C NH2 CH2SH
H2 N

S R

9.50
Which of the following pairs of structures represent the same enantiomers, and which represent
different enantiomers?
(a) (b)
Br CN COOH Br

H3C H H H
CN CH3 Br CN
H Br NC HOOC

(c) (d)
CH3 OH CH3 COOH

H H H H3C
OH CH2CH3 COOH H
H3CH2C H3C H2N H2N

Solution: (a) is different and (b), (c), (d) are the same.

9.51
Assign R or S configuration to each chirality center in the following molecules:
(a) (b)
H H H NH2
Br
H
H3C
COOH
CH3 H OH
Br
H
Solution: (a) (b)
H H H NH2
Br
H R
H3C S
COOH
S CH3 H
S
OH
Br
H

9.52
Draw tetrahedral representations of the following molecules.
(a) The 2S,3R enantiomer of 2,3-dibromopentane
(b) The meso form of 3,5-dichloroheptane.
H Br
(a) (b)

Br H H Cl H Cl
9.53 Draw the meso form of eachof the following molecules, and indicate the plane of
symmetry in each.
 H OH HO H
(a) (b) (c)

OH

The plane of symmetry The plane of symmetry The plane of symmetry

9.54 Assign R or S configurations to the chirality centers in ascorbic acid (vitamin c)

9.55:
Assign R or S sterochemistry to the chirality centers in the following Newman projections:
Cl H
H CH3 H3C OH
(a) (b)

H3 C H H3C CH3

H H

S R
9.56:
Xylose is a common sugar found in many types of wood, including maple and cherry. Because it
is much less prone to cause tooth decay than sucrose, xylose has been used in candy and chewing
gum. Assign R or S configuration to the chirality center in xylose.
HO H HO H

R S R
OHC CH2OH

HO H
9.57:
Ribose, an essential part of ribonucleic acid (RNA), has the following structure:
H H H OH

CHO
HO

HO H HO H

(a) How many chirality centers does ribose have? Identify them
 H H H OH

CHO
∗ ∗ ∗
HO

Solution: Three chirality centers. HO H HO H

(b) How many stereoisomers of ribose are there?

Solution: There are eight stereoisomers of ribose.
(c) Draw the structure of the enantiomer of ribose.
H H HO H

S CHO
S S
HO

H OH H OH
Solution:
(d) Draw the structure of a diastereomer of ribose.
Solution:
H H HO H H H H OH

S CHO S CHO
R S R R
HO HO

HO H H OH HO H H OH

H H HO H H H HO H

R CHO R CHO
R S S S
HO HO

HO H HO H H OH HO H

H H H OH H H H OH

R CHO S CHO
S R S R
HO HO

H OH HO H H OH H OH
9.58 On catalytic hydrogenation over a platinum catalyst, ribose (Problem 9.57) is converted into ribitol.
Is ribitol optically active or inactive? Explain.

H H H OH H H H OH
CHO CH2OH
HO HO
HO H HO H HO H HO H
Ribose Ribitol

S
H H H OH H OH
R S
C
HO H
HO H HO H
Ribitol

Solution: The product ribitol is optically inactive , because it is Meso compound.

9.59 Hydroxylation of cis-2-butene with OsO4 yields butane-2,3-diol. What steeochemistry do you expect
for the product?

O O

H3C CH3 Os
OsO4 O O NaHSO3
C C HO OH
Pyridine H2O
H H C C R S
C C
H H
H H
H3C CH3 H3C CH3

9.60:
Hydroxylation of cis-2-butene with OsO4 yields butane-2,3-diol. What steeochemistry do you expect
for the product?
Solution:

O O

H3C H Os
OsO4 O O NaHSO3
C C HO OH
Pyridine H2O
H CH3 C C R R
C C
H CH3 H CH3
H3C H H3C H

9.61
Alkenes undergo reaction with peroxycarboxylic acids (RCO3H) to give threemembered-ring cyclic
ethers called epoxices. For example, 4-octene reacts with a peroxyacid to yield 4,5-epoxyoctane:
 O
RCO3H
CH3CH2CH2 CH CHCH2CH2CH3 CH3CH2CH2CH CHCH2CH2CH3

4-Octene 4,5-Epoxyoctane
Assuming that this epoxidation reaction occurs with syn stereochemistry, draw the structure obtained
from epoxidation of cis-4-octene. Is the product chiral? How many chirality centers does it have? How
would you describe it stereochemically?
Solution:
S R

RCO3H

cis-Oct-4-ene cis-2,3-Dipropyl-oxirane

9.62
Answer Problem 9.61, assuming that the epoxidation reaction is carried out on trans-4-octene.
Solution:
R R
O
RCO3H

trans-Oct-4-ene
trans-2,3-Dipropyl-oxirane

9.63
Identify the indicated hydrogens in the following molecules as pro-R or pro-S:
H H H H H H

COOH H3 CS CO2 CO2

HOOC HS

H H H H
(a) HO H (b) H3N (c) H3N

Solution:
pro-R
pro-S
H
H

HO2C

CO2H

a) HO H
 pro-S por-R

H H

H3CS CO2

H H H3N H

b) pro-R pro-S
pro-S pro-R

H
H

HS

CO2

c) H3N H

9.64
Identify the indicated faces in the following molecules as re or si:

O
H
C C CH3
H3C CO2 O 2C C
(a) (b) H

Solution:
re
O

C
H3C CO2

(a) si
si

H
C CH3
O2C C
H

(b) re

9.65.
Write the products of following reaction and indicate the stereochemistry obtained in each
instance:
 Br2,H2O
(a) ?
DMSO

Br2
(b) ?
CH2Cl2

OsO4
(c) ?
NaHSO3
Solution:
H

Br2,H2O Br
(a)
DMSO
OH

H
H
Br2
(b)
CH2Cl2 Br

Br

H
H
OsO4
(c)
NaHSO3 OH

OH
9.66.
Draw all possible stereoisomers of cyclobutane-1,2-dicarboxylic acid, and indicate the
interrelationships. Which, if any, are optically active? Do the sane for
cyclobutane-1,3-dicarboxylic acid.
Solution: the stereoisomers of cyclobutane-1,2-dicarboxylic acid:
H COOH H
HOOC H H COOH HOOC COOH

COOH H H

1 2 3
1 and 2 are optically active.
the stereoisomers of cyclobutane-1,3-dicarboxylic acid:
 COOH H COOH
H HOOC H

H H COOH

COOH COOH H
They are all optically inactive.

9.67
Compound A, C7H12, was found to be optically active. On catalytic reduction over a palladium
catalyst, 2 equivalents of hydrogen were absorbed, yielding compound B, C7H16. On ozonolysis of
A, two fragments were obtained. One fragment was identified as acetic acid. The other fragment,
compound C, was an optically active carboxylic acid, C5H10O2.Write the reactions, and draw
structures for A, B, C.
Solution:
CH3 CH3 CH3

A. CH3C CCHC2H5 B. C3H7CHC2H5 C. C2 H5CHCO2H

CH3 CH3
2H2
CH3C CCHC2H5 C3H7CHC2 H5
Pd
CH3 CH3
O3 + CH3CO2H
CH3C CCHC2H5 C2H5CHCO2H

9.68
Compound A, C11H16O, was found to be an optically active alcohol. Despite its apparent
unsaturation, no hydrogen was absorbed on catalytic reduction over a palladium catalyst. On
treatment of A with dilute sulfuric acid, dehydration occurred and an optically inactive alkene B,
C11H14, was produced as the major product. Alkene B, on ozonolysis, gave two products. One
product was identified as propanal, C2H5CHO. Compound C, the other product, was shown to be a
ketone, C8H8O. How many degrees of unsaturation does A have? Write the reactions, and identify
A, B, and C.
Solution:
The degree of unsaturation of A is 4.
Ph

C2H5CHCHCH3 Ph O

A. OH B. C2H5 CH CCH3 C. CH3C Ph

 Ph Ph
H2SO4
C2H5CHCHCH3 C2H5CH CCH3

OH
Ph O O

O3
C2H5 CH CCH3
CH3 C Ph + C2H5CH

9.69
One of the steps in fat biosynthesis is the hydration of crotonate to yield 3-hydroxybutyrate. The
reaction occurs by addition of —OH to the si face at C3, followed by protonation at C2, also from the
si face. Draw the product of the reaction, showing the stereochemistry of each step.
3 OH
CO2
H3C H3 C CHCH2CO2
2

Solution:
H
3 H CO2 H
CO2
H3C H H3C
H3C 2 CO2

OH OH H

9.70
The dehydration of citrate to yield cis-aconitate, a step in the citric acid cycle, involves the pro-R “arm”
of citrate rather than the pro-S arm. Which of the following two products is formed?
HO CO2 CO2 CO2
or
O2C CO2 O2C CO2 O2C CO2

CO2

O2C CO2
Solution: This product is formed:

9.71
Hydration of cis-aconitate yields (2R, 3S)-isocitrate. Show the stereochemistry of the product, and
tell whether the addition of the OH group takes place on the re or si face of cis-aconitate.
 COO

COO
OOC COO
H2O
OOC COO
cis-Aconitate
OH

Isocitrate
Solution: the stereochemistry of the product as follow

O-

O H

O H

-O OH -O

And the OH group takes place on the re face of the cis-aconitate

9.72
The so-called tetrahedranes are an interesting class compounds, the first example of which was
synthesized in 1979. Make a model of a substituted tetrahedrane with four different substituents. Is
it chiral? Explain.

W Z Y
Solution:
It is chiral.because
X X

W Z Y Y Z W

I II

II is mirror-image of I, and they are enantiomers. Therefore I is chiral.

9.73
llenes are compounds with adjacent carbon-carbon double bonds. Many allenes are chiral, even though
they don’t contain chirality centers. Mycomycin, for example, a naturally occurring antibiotic
isolated from the bacterium Nocardia acidophilus, is chiral and has [α]D = -130º. Explain why
mycomycin is chiral. Making a molecular model should be helpful.

HC C C C C C C C C C C CH2CO 2H
H H H H H H
Mycomycin (an allene)

Solution:

According to the molecular model, we can see the atoms are arranged symmetrically
besides the carboxylic group. Except C1, there isn’t any symmetric element in the
molecule, so the molecule is chiral.

9.74

Long before chiral allenes were known , the resolution of 4-methylcyclohexylideneacetic acid
into two enantiomers had been carried out. Why is it chiral? What geometric similarity does it
have to allenes?

H CO2H

H3C H
methylcyclohexylideneacetic acid
Solution:
 The geometry of the acid is similar to the allene, the atoms are arranged symmetrically besides the
carboxylic group. Except C1, there isn’t any symmetric element in the molecule, so it is also chiral.

9.75
Suppose that racemic lactic acid reacts with methnol, CH3OH, to yield the ester, methyl lactate.
What stereochemistry would you expect the products to have? What is the relationship of one product
to another?

Solution:

H H

C C
HO COOH HO COOCH3

H3 C H3 C

S 50%
H3C OH S 50%

H H

C C
HO CH3 HO CH3

HOOC H3COOC

R 50%
R 50%

9.76
Suppose that (S)-lactic reacts with (R)-2-butanol to form an ester. What stereochemistry
would you expect the products to have?

Solution:
H
H H O

C C C
HO C H
HO COOH OH
H3 CH2C
H3C O C
H3C CH3
CH2 CH3

S R S CH3
R
9.77
Suppose that racemic lactic acid reacts with (S)-2-butanol to form an ester (Problem 9.76). What
stereochemistry does the product(s) have? What is the relationship of one product to another?
Assuming that esters can be converted back into carboxylic acids, how might you use this reaction to
resolve (±)-lactic acid?
Solution：
(1) The products are:
HO HO
CH3 CH3
H H
R H3C H S H3C H

CH3 CH3
S S
O O and O O

(2) They are diastereomers.

(3)
The diastereomers have different boiling point, so they can be separated by distillation. So we can
let the racemic lactic acid reacts with (S)-2-butanol to form these two esters, then separate them
by distillation, at last we can convert them back to (±)-lactic acid.

9.78
(S)-1-Chloro-2-methylbutane undergoes light-induced reaction with Cl2 by a radical mechanism to
yield a mixture of products. Among the products are 1,4-dichloro-2-methylbutane and
1,2-dichloro-2-mehylbutane.
(a)Write the reaction, showing the correct stereochemistry of the reactant.
(b)One of the two products is optically active, but the other is optically inactive. Which is which?
(c)What can you conclude about the stereochemistry of radical chlorination reactions?
Solution:
(a)
H3C H H3C Cl Cl CH3
+ Cl2 hv + Cl
CH3 Cl CH3 CH3
ClH2C

H3C H

+
Cl CH2Cl

(b)
1,2-dichloro-2-mehylbutane is optically inactive, because it is racemic.
(c)
Conclusion: when forming 1,2-dichloro-2-mehylbutane,half inversion occurs.
9.79
Draw the structure of a meso compound that has five carbons and three chirality centers.
Solution:
Sorry, I don’t know. I am wondering how can a meso compound which has odd chirality centers.
（my solution:

CH3 CH3
S R
H OH HO H
S H OH H OH R
R H OH HO H S
CH3 CH3
Both of them are meso-cpds,
because of the symmetrical plane
(C3-H-OH).
)
9.80
How many stereoisomers of 2,4-dibromo-3-chloropentane are there? Draw them, and indicate
which are optically active.
Solution:
Br Br Br Br

H3C H H CH3
H CH3 CH3 H
Cl Cl
(2R,4R)-Dibromo-3-chloro-pentane (2S,4S)-Dibromo-3-chloro-pentane

Br Br

H3C CH3
H H
Cl
(2R,4S)-Dibromo-3-chloro-pentane

The first two of them are optically active.

9.81
Draw both cis- and trans-1,3-dimethylcyclohexane in their most stable chair conformations.
(a) How many stereoisomers are there of cis-1,4-dimethylcyclohexane, and how many of
trans-1,4-dimethylcyclohexane?
(b) Are any of the structures chiral?
(c) Whar are the stereochemical relationships among the various stereoisomers of
1,4-dimethylcyclohexane?
Solution:
 CH3

CH3 CH3
H3C
CH3
CH3 trans
cis-1,4-dimethylcyclohexane trans-1,4-dimethylcyclohexane
(a) There is only one cis-1,4-dimethylcyclohexane and two
trans-1,4-dimethylcyclohexanes.
(b) Because of the existence of the symmetrical axes in cis or trans-1,4-dimethylcyclohexane,
neither of them have the structures chiral.
(c) They are diastereomers, in more detailed description, they are configurations and
Cis-trans diastereomers.
9.82
Draw both cis- and trans-1,3-dimethylcyclohexane in their most stable chair conformations.
(a) How many stereoisomers are there of cis-1,3-dimethylcyclohexane, and how many of
trans-1,3-dimethylcyclohexane?
(b) Are any of the structures chiral?
(c) Whar are the stereochemical relationships among the various stereoisomers of
1,3-dimethylcyclohexane?
Solution:

H 3C
CH3

cis-1,3-dimethylcyclohexane

H3C
CH3

CH3 CH3
(1S,3S)-1,3-dimethylcyclohexane (1R,3R)-1,3-dimethylcyclohexane
(a) There are one cis-1,3-dimethylcyclohexane and two trans-1,3-dimethylcyclohexanes.
(b) They are all chiral.
(c) They are diastereomers, in more detailed description, they are configurations and
Cis-trans diastereomers.

9.83
How can you explain the observation that cis-1,2-dimethylcyclohexane is optically inactive even it
has two chirality centers?
My Solutions :
 H
ring flip ring flip H ring flip H
H
CH3 H H 3C
H H H
H3C
CH 3 CH3
CH3 CH3 CH3

A B
H H

CH3 H 3C
H H racemic pairs
CH3 CH3
A B
The resolution of them is impossible, for the ring flip is
very fast.

9.84
An alkyl halide reacts with a nucleophile to give a substitution product by a mechanism that
involves inversion of stereochemistry at carbon:

Nu
C X
Nu C X
+

Formulate the reaction of (S)-2-bromobutane with HS- ion yield butane 2-thiol ,
CH3CH2CH(SH)CH3 .What is the stereochemistry of the product?

H
HS
Br
HS H

S R
My Solution:

9.85
Grignard reagents, RMgX, react with aldehaydes to yield alcohols. For example, the reaction of
methylmagnesium bromide with propanal yields 2-butanol:
O OH
1.CH3MgBr
H3CH2C C H H3CH2C C CH3
2.H3O+
H
(a) Is the product chiral? Is it optically active?
(b) How many stereoisomers of butanol are formed, what are their stereochemical relationships,
and what are their relative amounts?
Solution:
(a) The product id chiral and it’s optically active.
(b) A pair of enatiomers.
OH OH

C2H5 H H C 2H 5

CH3 CH3

(R)- 2-butanol (S)- 2-butanol

The ratio is 1 : 1

9.86
Imagine that another Grignard reaction similar to that in Problem 9.85 is carried out between
methylmagnesium bromide and (R)-2-phenylpropanal to yield 3-phenyl-2-butanol:
H CH3 OH

C O H
1.CH3MgBr H3C C C CH3
C H

H 2.H3 O+

(a) Is the product chiral? Is it optically active?

(b) How manystereoisomers of 3-phenyl-2-butanol are formed, what are their stereochemical
relationships ,and what are their relative amounts?
Solution:
(a) chiral product, optically active
(b)
H H

Ph CH3 Ph CH3

OH H H OH

CH3 CH3

（2S,3R）-3-Phenyl-2-butanol (2R,3R)-3-Phenyl-2-butanol
The ratio: 1 : 1
Meso-compound chiral product