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Chapter 9

Multiple Choice Questions:


Topic: Addition Reaction Mechanisms
Section: 9.1
Difficulty Level: Easy
1.

In an addition reaction to an alkene, the bond plays the role of:


A)
nucleophile
B)
electrophile
C)
leaving group
D)
A and B
E)
B and C
Ans: A

Topic: Addition Reaction Mechanisms


Section: 9.1
Difficulty Level: Moderate
2.

Addition reactions of alkenes are characterized by:


A)
formation of a bond
B)
addition of two groups across a double bond
C)
breaking of a bond
D)
A and B
E)
B and C
Ans: E

Topic: Addition vs. Elimination Thermodynamic Perspective


Section: 9.2
Difficulty Level: Easy
3.

The decrease in entropy (the S value is negative) observed for alkene addition
reactions results from:
A)
the breaking of a and bond.
B)
the formation of two bonds.
C)
the reaction being exothermic.
D)
two molecules reacting to form a single molecule.
E)
the temperature dependence of the S term.
Ans: D

Topic: Addition vs. Elimination Thermodynamic Perspective


Section: 9.2
Difficulty Level: Easy
4.

In a reaction where addition and elimination reactions are in competition, which of


the following statements is most correct?
A)
Addition and elimination reactions are favored at low temperatures.
B)
Addition and elimination reactions are favored at high temperatures.
C)
Only addition reactions are favored at low temperatures.
D)
Only elimination reactions are favored at low temperatures.
E)
Addition and elimination reactions are disfavored at low temperatures.
Ans: C

Topic: Addition vs. Elimination Thermodynamic Perspective


Section: 9.2
Difficulty Level: Easy
5.

Which statement is true about the temperature dependence of an addition reaction?


A)
Addition reactions are thermodynamically favorable at all temperatures.
B)
Addition reactions are thermodynamically disfavored at all temperatures.
C)
Addition reactions are thermodynamically favorable at low temperatures.
D)
Addition reactions are thermodynamically favorable at high temperatures.
E)
Addition reactions are thermodynamically impossible.
Ans: C

Topic: Addition vs. Elimination Thermodynamic Perspective


Section: 9.2
Difficulty Level: Moderate
6.

For an addition reaction, why does the free energy term, G, become more positive
with increasing temperature?
A)
The positive entropy term dominates at high temperature.
B)
The negative entropy term dominates at high temperature.
C)
The positive enthalpy term dominates at high temperature.
D)
The negative enthalpy term dominates at high temperature.
E)
The enthalpy and entropy terms cancel at high temperature.
Ans: A

Topic: Addition vs. Elimination Thermodynamic Perspective


Section: 9.2
Difficulty Level: Hard
7.

Addition reactions are favorable at low temperatures because:


A)
the positive enthalpy term is larger than the negative entropy term.
B)
the negative enthalpy term is larger than the positive entropy term.
C)
the positive enthalpy term is smaller than the negative entropy term.
D)
the negative enthalpy term is smaller than the positive entropy term.
E)
the enthalpy and entropy terms are equal.
Ans: B

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
8.

Which of the molecules below would be the expected product for


hydrohalogenation of the following alkene:

A)
B)
C)
Br

D)

Br
Br

E)
Ans:

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
9.

In the addition reaction of HI to 2-methyl-2-butene, the Markovnikov addition


mechanism involves:
A)
attack of 2-methyl-2-butene initiated by an iodide ion.
B)
attack of 2-methyl-2-butene initiated by an iodine atom.
C)
isomerization of 2-iodo-2-methylbutene.
D)
formation of a carbocation at carbon two (C-2).
E)
formation of carbocation at carbon three (C-3).
Ans: D

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
10.

The expected Markovnikov addition product of HI to 2-methyl-2-butene is:


A)
2-iodopentane
B)
2-iodo-2-methylbutane
C)
1-iodo-2-methylbutane
D)
2-iodo-1-methylbutane
E)
3-iodo-2-methylbutane

Ans: B
Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
11.

The regioselectivity and stereospecificity in hydrohalogenation of an alkene is best


described as:
A)
Markovnikov orientation with syn-addition
B)
Markovnikov orientation with anti-addition
C)
anti-Markovnikov orientation with syn-addition
D)
anti-Markovnikov orientation with anti-addition
E)
Markonikov orientation with both syn- and anti-addition
Ans: E

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
12.

Which of the structures shown depicts the most stable carbocation intermediate
formed in a hydrohalogenation reaction?
CH2

A)
B)
C)
D)
E)
Ans:

I
II
III
IV
V
B

CH3

CH3

CH3

CH3

II

III

IV

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
13.

What compound is the expected product upon Markovnikov hydrohalogenation


with HBr of the alkene shown below?

Br

A)
Br

B)

C)
D)

Br
Br
Br

E)
Ans:

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
14.

The expected major product of the following reaction is:


HBr

Br

A)
Br

B)
Br

C)

Br

D)
Br

E)
Ans:

Br

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
15.

The expected major product of the following reaction is:


HBr
ROOR
Br

A)
B)
Br

C)
Br

D)
Br

E)
Ans:

Br

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
16.

What is the expected major product for the following reaction?


HBr
ROOR

Br
Br
I

A)
B)
C)
D)
E)
Ans:

II

I
II
III
IV
V
D

Br
III

Br
IV

Topic: Anti-Markovnikov Hydrohalogenation


Section: 9.3
Difficulty Level: Easy
17.

Which of the molecules below arises from anti-Markovnikov hydrohalogenation


with HBr of the alkene shown?

Br

A)
Br

B)
C)

Br

D)
E)
Ans:

Br

Br

Topic: Stereochemistry of Hydrohalogenation


Section: 9.3
Difficulty Level: Easy
18.

Which of the alkenes shown below would produce a chirality center upon
hydrohalogenation?

A)
B)
CH3

C)
D)

E)
Ans:

Topic: Stereochemistry of Hydrohalogenation


Section: 9.3
Difficulty Level: Easy
19.

What is the major product for the following reaction?


HI

A)
B)

C)

I
I

D)

E)
Ans:

Topic: Stereochemistry of Hydrohalogenation


Section: 9.3
Difficulty Level: Moderate
20.

Which of the alkenes below would be expected to produce a chirality center upon
hydrohalogenation in the presence of peroxide?
A)
B)
C)
D)
E)
Ans:

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Moderate
21.

Which of the given reaction schemes would produce the molecule shown below?

Br
HBr
ROOR

A)

HBr

B)
HBr

C)
D)
E)
Ans:

ROOR

Both A and B
Both B and C
E

Topic: Stereochemistry of Hydrohalogenation


Section: 9.3
Difficulty Level: Moderate
22.

Which of the molecules below are enantiomers, formed as products upon reaction
of HBr with 4-methylpent-1-ene?
Br H
Br H

H Br

A)
B)
C)
D)
E)
Ans:

H Br

II

I and II
II and III
III and IV
I and III
II and IV
E

III

IV

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate
23.

Which of the following carbocations is likely to undergo rearrangement through a


methyl shift?
H2C CH3

H3C CH3

H3C CH3

II

III

A)
B)
C)
D)
E)
Ans:

I
II
III
I and II
II and III
D

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate
24.

Which of the following carbocations is likely to undergo rearrangement through a


hydride shift?
CH2

A)
B)
C)
D)
E)
Ans:

CH3

II

I
II
III
I and II
II and III
D

CH2

III

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate
25.

The expected major product(s) of HCl addition to the alkene shown would be:
HCl

Br
Cl

Cl

Cl

Cl
Cl

Br

Br

Br

Br

Br

II

III

IV

A)
B)
C)
D)
E)
Ans:

I and II
II and III
I and IV
V
All of the above are equally likely to form
A

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate
26.

The expected major product(s) of HBr addition to the alkene shown would be:
HBr
Br

A)

B)

+ enantiomer

Br

Br

C)

+ enantiomer

Br

Br

D)

Br

E)
Ans:

Topic: Stereochemistry of Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate
27.

The reaction shown below would be expected to produce as major products which
of the following compounds?
HCl

+ enantiomer

A)

Cl
+ enantiomer

B)

Cl

Cl

C)

+ enantiomer

Cl
+ enantiomer

D)
+ enantiomer

E)
Ans:

Cl

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Hard
28.

What is the IUPAC name of the expected major product formed upon reaction of
HCl with 3-methyl-1-butene?
A)
1-Chloro-2-methylbutane
B)
1-Chloro-3-methylbutane
C)
2-Chloro-2-methylbutane
D)
2-Chloro-3-methylbutane
E)
1-Chloropentane
Ans: C

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Hard
29.

Select the expected major product(s) of the following reaction:


HBr

?
Br

A)
Br

B)
C)
D)
E)
Ans:

Br

A and B
A and C
C

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Hard
30.

Identify the expected product(s) for the reaction shown below?


HBr

+ enantiomer

A)
B)

Br

Br

+ enantiomer

C)

Br
Br

+ enantiomer

D)
Br
+ enantiomer

E)
Ans:

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy
31.

The regioselectivity and stereospecificity in the acid-catalyzed hydration of an


alkene is best described as:
A)
Markovnikov orientation with syn-addition
B)
Markovnikov orientation with anti-addition
C)
anti-Markovnikov orientation with syn-addition
D)
anti-Markovnikov orientation with anti-addition
E)
Markonikov orientation with both syn- and anti-addition
Ans: E

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy
32.

The expected major product of the following reaction is:


H+

H2O
OH

OH

OH

OH
OH
I

A)
B)
C)
D)
E)
Ans:

II

I
II
III
IV
V
D

III

IV

OH

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy
33.

The expected major product of the following reaction is:


H3O+
H2O
OH
OH
I

A)
B)
C)
D)
E)
Ans:

II

OH
III

OH
IV

I
II
III
IV
V
C

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy
34.

The expected major product of the following reaction is:


H 3O +

OH
OH

A)
OH

B)
C)
D)
E)

OH

OH

OH

OH

Ans: D
Topic: Acid Catalyzed Hydration
Section: 9.4
Difficulty Level: Easy
35.

Treatment of 1-methylcyclohexene with H3O+ would be expected to yield as the


major product which of the molecules below?

HO

HO
HO

HO
I

A)
B)
C)
D)
E)
Ans:

OH

II

III

IV

I and III
II
III and V
IV
I, III and V
D

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Moderate
36.

Treatment of (S)-6-chloro-1-methyl-1-cyclohexene with H3O+ is expected to


produce which of the following?
OH
OH
OH

OH
Cl
I

A)
B)
C)
D)
E)
Ans:

Cl

Cl

Cl OH

Cl

II

III

IV

I and III
II
III and V
IV
I, III and V
B

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Hard
37.

What is the expected major product for the following reaction?


MeOH
[H2SO4]

A)

OMe

+ enantiomer

B)

OMe
OMe
+ enantiomer

C)
+ enantiomer

D)

OMe
OMe

+ enantiomer

E)
Ans:

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy
38.

The regioselectivity and stereospecificity in the oxymercuration-demercuration of


an alkene is best described as:
A)
Markovnikov orientation with syn-addition
B)
Markovnikov orientation with anti-addition
C)
anti-Markovnikov orientation with syn-addition
D)
anti-Markovnikov orientation with anti-addition
E)
Markonikov orientation with both syn- and anti-addition
Ans: B

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy
39.

What is the expected major product for the following reaction?


1. Hg(OAc)2, H2O
2. NaBH4, NaOH

A)
OH
+ enantiomer

B)
OH
HO
+ enantiomer

C)
HO

D)
HO

E)
Ans:

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy
40.

What synthetic goal is achieved by subjecting an alkene to an oxymercurationdemercuration reaction sequence?


A)
Markovnikov addition of H2O, promoting skeletal rearrangement
B)
Markovnikov addition of H2O, preventing skeletal rearrangement
C)
anti-Markovnikov addition of H2O, promoting skeletal rearrangement
D)
anti-Markovnikov addition of H2O, preventing skeletal rearrangement
E)
anti-Markovnikov addition of H2O, syn-hydroxylation
Ans: B

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy
41.

What is the expected major product for the following reaction?


1. Hg(OAc)2, H2O
2. NaBH4, NaOH
O
H

A)

+ enantiomer

B)

OH
OH

C)
+ enantiomer

D)

OH

OH

E)
Ans:

OH

+ enantiomer

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy
42.

What is the expected major product for the following reaction?


1. Hg(OAc)2, H2O
2. NaBH4, NaOH
OH

+ enantiomer

A)
OH
+ enantiomer

B)

OH
OH
+ enantiomer

C)
+ enantiomer

D)

HO
OH

+ enantiomer

E)
Ans:

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Easy
43.

What is the expected major product for the following reaction?


1. Hg(OAc)2, EtOH
2. NaBH4, NaOH

A)

B)
C)

HO

D)

E)
Ans:

+ CO2
O

OH

Topic: Oxymercuration-Demercuration
Section: 9.5
Difficulty Level: Moderate
44.

When an alkene is subjected to treatment with Hg(OAc)2 in alcohol, followed by


reaction with NaBH4, what functional group is formed?
A)
ether
B)
epoxide
C)
alkane
D)
syn diol
E)
alkyne
Ans: A

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy
45.

The regioselectivity and stereospecificity in the hydroboration-oxidation of an


alkene is best described as:
A)
Markovnikov orientation with syn-addition
B)
Markovnikov orientation with anti-addition
C)
Anti-Markovnikov orientation with syn-addition
D)
Anti-Markovnikov orientation with anti-addition
E)
Markovnikov orientation with both syn- and anti-addition
Ans: C

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy
46.

What reagents are needed to accomplish the following transformation?


CH3

A)
H2O/H+
B)
H2O/Peroxide
C)
OH
D)
BH3
E)
1. BH3, 2. HO, H2O2, H2O
Ans: E

CH3
OH !

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy
47.

What is the expected major product for the following reaction sequence?
1. BH3THF
2. H2O2, NaOH

+ enantiomer

A)

OH

B)
C)

OH

D)

OH

E)
Ans:

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy
48.

What is the expected major product for the following reaction sequence?
1. BH3THF
2. H2O2, NaOH
OH
OH
OH
+
enantiomer

+
enantiomer

+
enantiomer

II

III

A)
B)
C)
D)
E)
Ans:

I
II
III
I and II
I and III
E

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Moderate
49.

What is the expected major product for the following reaction sequence?
1. BH3THF
2. H2O2, NaOH

OH + enantiomer

A)

OH
O
H

B)

+ enantiomer

C)

OH

D)

OH

+ enantiomer

E)
Ans:

OH

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Moderate
50.

What is the expected major product for the following reaction sequence?
1. BD3THF
2. H2O2, NaOH

OH
+
enantiomer
I

A)
B)
C)
D)
E)
Ans:

HO

OH

+
enantiomer

+
enantiomer

+
enantiomer

II

III

IV

I
II
III
IV
V
D

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Moderate
51.

What is the expected major product for the following reaction sequence?
1. BH3THF
2. H2O2, NaOH

A)

HO
HO
+ enantiomer

B)
HO
+ enantiomer

C)
OH

D)
HO

E)

HO

+
enantiomer

+ enantiomer

Ans:

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
52.

What is the expected major product for the hydrogenation of an alkene?


A)
dihaloalkane
B)
alkane
C)
haloalkane
D)
alcohol
E)
ether
Ans: B

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
53.

Provide the major organic product(s) for the reaction shown below.
H2, Pd/C
Pd

?!

A)
B)
OH

C)

OH

D)
E)
Ans:

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
54.

What product is formed when 5-chloro-1-methylcyclohexene is reduced with a Pt


catalyst and H2?
A)
1-chloro-5-methylcyclohexane
B)
1-chloro-3-methylcyclohexane
C)
5-chloro-1-methylcyclohexane
D)
3-chloro-1-methylcyclohexane
E)
None of the above

Ans: B
Topic: Catalytic Hydrogenation
Section: 9.7
Difficulty Level: Easy
55.

What product is formed when trans-1,2-dimethylcyclohexane is reacted with Pd/C


and H2?
A)
No reaction
B)
cis-1,2-dimethylcyclohexane
C)
trans-3,4-dimethylhexane
D)
trans-1,2-dimethylhexane
E)
None of the above
Ans: A

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
56.

Which of the following reagents accomplishes the transformation shown below?


?

A)
B)
C)
D)
E)
Ans:

H2/HCl
H2/H2SO4
H2/Ni
H2O/Ni
H2O/H2SO4
C

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
57.

Which of the reagents below are expected to convert cyclopentene into


cyclopentane?
A)
H2 and Ni
B)
H2 O
C)
Heat
D)
Zn, H3O+
E)
Light
Ans: A

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
58.

Which alkene would yield 3-methylpentane upon subjection to catalytic


hydrogenation?

A)
B)
C)
D)
E)
Ans:

I
II
III
IV
V
B

II

III

IV

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
59.

How many moles of hydrogen (H2) are consumed in the catalytic reduction of 1
mole of 1,3-dibromocyclohexa-1,4-diene?
A)
1
B)
2
C)
3
D)
4
E)
None of the above
Ans: B
2

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
60.

How many moles of hydrogen (H2) are required to completely reduce 1 mole of
cis-2,3,3-trimethylhepta-1,5-diene?
A)
0
B)
1
C)
2
D)
3
E)
4
Ans: C
2

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
61.

Which of the catalysts listed are used in the homogenous catalytic hydrogenation of
alkenes?
I) Ni
II) Pt
III) Wilkinson
A)
B)
C)
D)
E)
Ans:

I
II
III
I and II
II and III
C

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
62.

In conducting a catalytic hydrogenation of an alkene, which catalyst listed is most


likely soluble in the reaction medium?
A)
Ni
B)
Pt
C)
Pd
D)
Wilkinson
E)
All of the above are soluble
Ans: D

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
63.

Wilkinsons catalyst accomplishes which of the listed molecular transformations?


A)
syn addition of H2 to an alkene
B)
anti addition of H2 to an alkene
C)
syn dihydroxylation of an alkene
D)
anti dihydroxylation of an alkene
E)
oxidative cleavage of an alkene
Ans: A

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Easy
64.

For the catalytic hydrogenation of alkenes, select from below those most likely to
function as a homogenous catalyst?
A)
Wilkinson
B)
Ni
C)
Pd
D)
Pt
E)
Au
Ans: A

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Moderate
65.

Which of the following will yield 2-methylpentane upon catalytic hydrogenation?


A)
2-methyl-1-pentene
B)
2-methyl-2-pentene
C)
4-methyl-2-pentene
D)
4-methyl-1-pentene
E)
All of the above
Ans: E
2

Topic: Catalytic Hydrogenation


Section: 9.7
Difficulty Level: Moderate
66.

For the complete reduction of 1 mole of (3E,5E)-hepta-1,3,5-triene with H2 using a


Pd catalyst, how many moles of H2 are consumed?
A)
1
B)
2
C)
3
D)
4
E)
5
Ans: C

Topic: Catalytic Hydrogenation and Stereospecificity


Section: 9.7
Difficulty Level: Moderate
67.

What products are produced from the reaction below?


H2

Pt

II

A)
B)
C)
D)
E)
Ans:

III

IV

I, II, III
II, III, IV
I and IV
II and III
I, II, III, and IV
A

Topic: Catalytic Hydrogenation and Stereospecificity


Section: 9.7
Difficulty Level: Moderate
68.

Identify the major organic product generated from the reaction shown.!
D2
Pd
D
CH3

CH3
D

+
enantiomer
I

A)
B)
C)
D)
E)
Ans:

+
enantiomer
II

I
II
III
IV
V
B

CH3
H

CH3
D
D

+
enantiomer

+
enantiomer

III

IV

CH3
D

+
enantiomer
V

Topic: Halogenation
Section: 9.8
Difficulty Level: Easy
69.

Which reaction intermediate is formed when 4-methylcyclohexene reacts with Br2


dissolved in CCl4?
Br

Br

Br
Br
H 3C
I

A)
B)
C)
D)
E)
Ans:

H3C

H 3C
II

Br
III

Br
IV

I
II
III
IV
V
B

Topic: Halogenation
Section: 9.8
Difficulty Level: Easy
70.

What is the expected major product upon reaction of 1-pentene with Cl2?
A)
1-chloropentane
B)
2-chloropentane
C)
1,1-dichloropentane
D)
2,2-dichloropentane
E)
1,2-dichloropentane
Ans: E

Topic: Halogenation and Stereospecificity


Section: 9.8
Difficulty Level: Easy
71.

Treating 2-methyl-2-pentene with Br2 is expected to produce which of the


following as the major product?
A)
2,3-dibromo-2-methylpentane
B)
2,2-dibromo-2-methylpentane
C)
3,3-dibromo-2-methylpentane
D)
2-bromo-2-methylpentane
E)
3-dibromo-2-methylpentane
Ans: A

Topic: Halohydrin Formation


Section: 9.8
Difficulty Level: Easy
72.

The expected intermediate formed during a halohydrin reaction is:


A)
a halonium ion.
B)
the most stable carbocation with OH on the adjacent carbon.
C)
the most stable carbocation with X on the adjacent carbon.
D)
a cyclic oxonium ion.
E)
the most stable carbanion.
Ans: A

Topic: Halohydrin Formation


Section: 9.8
Difficulty Level: Easy
73.

What major product is expected from the following reaction?


Br2

H2O
OH

Br

Br

A)
B)
C)
D)
E)
Ans:

OH

Br

OH

Br

Br

OH
II

I
II
III
IV
V
D

Br

III

IV

Topic: Halohydrin Formation


Section: 9.8
Difficulty Level: Moderate
74.

What is the expected major product for the following reaction?


Br2, CH3OH

OH

Br

OCH3

H3CO
Br
+
enantiomer
I

A)
B)
C)
D)
E)
Ans:

I
II
III
IV
V
D

Br
+
enantiomer

OCH3

Br

+
enantiomer

+
enantiomer
III

II

H3CO

Br

IV

Topic: Halogenation and Stereospecificity


Section: 9.8
Difficulty Level: Moderate
75.

Which of the statements is most correct regarding the products expected from the
halogenation reaction shown below?
Br2, CCl4

CH3
H
Br
Br
H

CH3

C2H5

H
Br
C2H5

II

A)
B)
C)
D)
E)
Ans:

Br
H

H
H

?
CH3
Br
Br

Br
Br

CH3
H
H

C2H5

C2H5

III

IV

Equal amounts of I and II are produced.


Equal amounts of III and IV are produced.
Equal amounts of I and IV are produced.
Equal amounts of II and III are produced.
Equal amounts of I and III are produced.
B

Topic: Halogenation and Stereospecificity


Section: 9.8
Difficulty Level: Moderate
76.

For the halogenation reaction shown below, which of the following statements is
correct regarding the expected products?
I2, CCl4

C2H5
I
CH3
I
H

C2H5
H3C
I
H
I

?
C2H5

C2H5
H3C
I
I
H

C2H5

C2H5

C2H5

CH3
I
C2H5

II

III

IV

A)
B)
C)
D)
E)
Ans:

I
H

Equal amounts of I and II produced


Equal amounts of III and IV produced
Equal amounts of I and IV produced
Equal amounts of II and III produced
Equal amounts of I and III produced
A

Topic: Halogenation, Regioselectivity, and Stereospecificity


Section: 9.8
Difficulty Level: Hard
77.

The reaction of Br2 with 1-methylcyclohexene, in the presence of ethylamine


(EtNH2), is expected to produce which of the following as the major product?
CH3
Br

CH3
NHEt

NHEt
+
enantiomer

Br
+
enantiomer

A)
B)
C)
D)
E)
Ans:

I
II
III
IV
V
D

II

CH3
Br
NHEt
+
enantiomer
III

CH3
NHEt

Br

Br
+
enantiomer
IV

NHEt

Topic: anti dihydroxylation


Section: 9.9
Difficulty Level: Easy
78.

For the reaction sequence below, identify the expected major products.
1. MCPBA
2. H3O+

O
+ enantiomer

A)
OH
+ enantiomer

B)

OH

OH
+ enantiomer

C)

HO
OH

D)

+ enantiomer

OH

OH
+ enantiomer

E)
Ans:

OH

Topic: anti dihydroxylation


Section: 9.9
Difficulty Level: Moderate
79.

For the reaction sequence below, identify the expected major product(s).
1. MCPBA
2. H+, H2O
HO

H3CH2C

H
CH2CH3
OH

A)
B)
C)
D)
E)

I
II
III
I and III
II and III

H
CH2CH3

HO
H
H3CH2C

OH
II

CH2CH3
H

HO
H
H3CH2C

OH
III

Ans: D
Topic: anti dihydroxylation
Section: 9.9
Difficulty Level: Moderate
80.

What are the major products for the following reaction sequence?
1. MCPBA

CH3

2. H3O+

CH3

CH3
OH
OH

OH
OH
I

A)
B)
C)
D)
E)
Ans:

OH

OH
OH
CH3

II

III

CH3
OH
IV

I and II
II and III
III and IV
I and III
II and IV
E

Topic: anti dihydroxylation


Section: 9.9
Difficulty Level: Moderate
81.

What is the major product for the following reaction sequence?


1. MCPBA

2. [H2SO4], CH3OH
OH

OH

OCH3

OCH3

H3CO
OCH3

OH

+
enantiomer

+
enantiomer

II

A)
B)
C)
D)
E)

I
II
III
IV
V

OCH3
+
enantiomer
III

OH
+
enantiomer
IV

OCH3
+
enantiomer
V

Ans: D
Topic: anti dihydroxylation
Section: 9.9
Difficulty Level: Hard
82.

For the following dihydroxylation reaction which of the following statements is


correct regarding the expected products?
1. MCPBA
2. H3O+
CH(CH3)2
H3CH2C
OH
H
OH

A)
B)
C)
D)
E)
Ans:

H3CH2C
HO

CH(CH3)2
OH
H

HO
HO

CH(CH3)2
CH2CH3
H

CH(CH3)2
HO
H

CH2CH3

CH2CH3

CH2CH3

CH2CH3
OH
CH2CH3

II

III

IV

Equal amounts of I and II produced


Equal amounts of III and IV produced
Equal amounts of I and IV produced
Equal amounts of II and III produced
Equal amounts of I and III produced
E

Topic: anti dihydroxylation


Section: 9.9
Difficulty Level: Hard
83.

An unknown alkene was reacted with MCPBA in dichloromethane, followed by


work-up with H2O/H+. A racemic mixture of the compound shown below was
obtained. What is correct name of the starting alkene?
OH
+ enantiomer
OH

A)
B)
C)
D)
E)
Ans:

(Z)-3-methylpent-2-ene
(E)-3-methylpent-2-ene
2-methylpent-2-ene
2,3-dimethylbut-2-ene
none of the above
A

Topic: syn Dihydroxylation


Section: 9.10
Difficulty Level: Easy
84.

Identify the expected major organic product resulting from the following reaction
sequence.
1. KMnO4, NaOH
Cold

OH

A)
B)
C)
D)
E)
Ans:

OH

OH

I
II
III
IV
V
A

O
OH
OH

OH
II

H
H

III

IV

Topic: syn Dihydroxylation


Section: 9.10
Difficulty Level: Easy
85.

Treatment of 1,2-dimethylcyclopentene with OsO4, followed by aqueous NaHSO3,


produces which of the following:
OH
CH3

OH
CH3

OH
CH3

CH3
H

CH3
H

CH3
OH

OH
CH3

H
CH3

OH
CH3

H
CH3

A)
B)
C)
D)
E)
Ans:

II

I
II
III
IV
V
A

III

IV

Topic: syn Dihydroxylation


Section: 9.10
Difficulty Level: Easy
86.

Identify the expected major organic product generated from the reaction sequence
shown.!
1) OsO4
2) NaHSO3/H2O
OH
CH3

CH3
OH

OH
+
enantiomer
I

A)
B)
C)
D)
E)
Ans:

OH
+
enantiomer

I
II
III
IV
V
B

II

CH3
H

CH3
OH
OH
+
enantiomer
III

CH2OH
OH

OH
+
enantiomer
IV

+
enantiomer
V

Topic: syn Dihydroxylation


Section: 9.10
Difficulty Level: Easy
87.

Which of the following alkene addition reactions occur(s) specifically in syn


fashion?
A)
dihydroxylation using OsO4, H2O2
B)
addition of H2
C)
hydroboration
D)
addition of HCl
E)
A, B, and C
Ans: E

Topic: syn Dihydroxylation


Section: 9.10
Difficulty Level: Easy
88.

What is the expected major product for the following reaction sequence?
1. OsO4, pyridine
2. H2O, NaHSO3
OH
+ enantiomer

A)

OH
OH
+ enantiomer

B)

OH
H

C)

O
OH

D)
E)
Ans:

O
+

HO

None of the above


A

Topic: Oxidative Cleavage


Section: 9.11
Difficulty Level: Easy
89.

Provide the expected major organic product of the reaction sequence shown.
1. O3

2. (CH3)2S, (DMS)

A)
B)
C)
D)
E)

O
II

I and II
IV and V
I only
II only
III only

III

O
IV

O
V

Ans: E
Topic: Oxidative Cleavage
Section: 9.11
Difficulty Level: Easy
90.

Which of the following reagents effectively cleaves a carbon-carbon double bond?


A)
Cl2/h
O

B)
C)
D)
E)
Ans:

H2SO4
cold KMnO4
O3/DMS
E

Topic: Oxidative Cleavage


Section: 9.11
Difficulty Level: Moderate
91.

How many carbonyls are generated upon treatment of the molecule below with
ozone, followed by zinc metal and water?

A)
B)
C)
D)
E)
Ans:

1
2
3
4
8
E

Topic: Oxidative Cleavage


Section: 9.11
Difficulty Level: Moderate
92.

Of the alkenes shown, which would produce the product shown below, upon
treatment with ozone, followed by zinc metal and water?
H H HH H O
H
C
C
C
C
H
C
C
C
H
O H HH H

CH3

A)
B)
C)
D)
E)
Ans:

II

CH3

CH3

III

IV

I
II
III
IV
V
B

Topic: Oxidative Cleavage


Section: 9.11
Difficulty Level: Moderate
93.

What is the expected major product of the reaction sequence shown below?
CH3

1. O3

2. Zn/H2O

H3C

O
H

H 3C

CH3
H

CH3 O

O
H

OH

O
I

A)
B)
C)
D)
E)
Ans:

I
II
III
IV
V
A

II

III

IV

Topic: Oxidative Cleavage


Section: 9.11
Difficulty Level: Moderate
94.

What are the expected major products from the reaction sequence shown below?
1. O3

2. Zn/H2O
O

O
C

O C O
H

A)
B)
C)
D)
E)
Ans:

II

I
II
III
IV
V
A

CO2H

III

OH

H
IV

OH

HO
V

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Easy
95.

Which of the following alkene addition reactions occur(s) specifically in an anti


fashion?
A)
hydroboration-oxidation
B)
addition of Br2
C)
addition of H2
D)
addition of H2O in dilute acid
E)
both A and B
Ans: B

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Easy
96.

The Markovnikov product, resulting from an addition reaction to an unsymmetrical


alkene, is formed because:
A)
the product is statistically favored.
B)
steric hindrance favors its formation.
C)
the reaction proceeds via the more/most stable carbocation.
D)
the reaction forms the more/most stable product.
E)
All of the above are valid reasons
Ans: C

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Easy
97.

What is the expected major product for the following reaction sequence?
1. BH3THF
2. H2O2, NaOH

OH

A)
O

B)

+ CO2

OH

C)
D)

OH

E)

OH

+ enantiomer
OH

+ enantiomer

Ans: A
Topic: Predicting Addition Products
Section: 9.12
Difficulty Level: Easy
98.

What reagents are most likely to accomplish the transformation shown below?
?

A)
B)
C)
D)
E)
Ans:

OH

1. BH3 / 2. HO, H2O2, H2O


H+ , H2 O
1. Hg(OAc)2, H2O, THF / 2. NaBH4
1. Hg(OAc)2, CH3OH / 2. NaBH4
NaOH, H2O
A

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Easy
99.

Which reaction is not stereospecific?


trans-2-Butene

Br2/CCl4

cis-2-Pentene

Br2/H2O

trans-2-Hexene
1-Methylcyclohexene
2-Methyl-2-heptene

A)
B)
C)
D)
E)
Ans:

I
II
III
IV
V
C

HBr
D2/Pd
KMnO4, NaOH
Cold

I
II
III
IV
V

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Moderate
100. The expected product(s) resulting from addition of Br2 to (E)-3-hexene would be:
A)
a meso dibromide.
B)
a mixture of optically active enantiomeric dibromides.
C)
a mixture of optically inactive enantiomeric dibromides.
D)
(Z)-3,4-dibromo-3-hexene.
E)
(E)-3,4-dibromo-3-hexene.
Ans: A
Topic: Predicting Addition Products
Section: 9.12
Difficulty Level: Moderate
101. Which of the following alkenes will yield a meso dihalide when reacted with
Br2/CCl4 at room temperature?

A)
B)
C)
D)
E)
Ans:

Both B and D
B

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Moderate
102. What is the expected major product resulting from the acid-catalyzed hydration of
2,5-dimethyl-2-hexene?
A)
B)

HO

HO
OH

C)

D)

E)
Ans:

OH
OH
HO

Topic: Predicting Addition Products


Section: 9.12
Difficulty Level: Hard
103. What is the expected major product resulting from treatment of (E)-3-methyl-3hexene with Br2 in the presence of methanol, CH3OH?
Br

A)

B)

OMe
Br
MeO
OMe

C)

D)
E)
Ans:

Br
OMe
Br

All of the above are produced in equal amounts


A

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Easy
104. To accomplish a Markovnikov addition of water to an unsymmetrical alkene, with
minimal skeletal rearrangement, the best reagents would be:
A)
water and dilute acid
B)
water and concentrated acid
C)
1. Hg(OAc)2, H2O
2. NaBH4, NaOH
D)
1. BH3THF
2. H2O2, NaOH
E)
1. OsO4, pyridine
2. NaHSO3, H2O
Ans: C
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Easy
105. For the reaction sequence shown, what is the expected major elimination product?
1. HI
2. NaOMe, MeOH

I
O

A)
B)
C)
D)
E)
Ans:

II

I
II
III
IV
V
B

III

IV

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Easy
106. For the reaction sequence shown, what is the expected major elimination product?
1. HBr
2. NaOMe, MeOH

A)
B)
C)
D)
E)
Ans:

II

III

IV

I
II
III
IV
V
D

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Easy
107. What is the expected major product of the following reaction sequence?
1. HCl
2. t-BuOK, t-BuOH

O
I

A)
B)
C)
D)
E)
Ans:

II

I
II
III
IV
V
C

III

IV

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Moderate
108. What is the expected major product of the following reaction sequence?
Br

1. NaOEt, HOEt, heat


2a. Hg(OAc)2, CH3OH
2b. NaBH4, NaOH
OCH3

OH
H3C

OCH3
I

A)
B)
C)
D)
E)
Ans:

OH
II

III

IV

I
II
III
IV
V
A

Topic: Synthetic Strategies, anti Dihydroxylation


Section: 9.13, 9.9
Difficulty Level: Moderate
109. Which is the correct sequence of reaction steps necessary to complete the following
transformation?
Br

OH
+ enantiomer
OH

I. MCPBA

A)
B)
C)
D)
E)
Ans:

II. NaOCH2CH3, CH3CH2OH

I then II then III


II then I then III
II then IV
III then I
I then IV then II then III
B

III. H3O+ or -OH

IV. 1) OsO4 then 2) NaHSO3/H2O

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Moderate
110. What is the expected major product of the following reaction sequence?
1. NaOEt, EtOH, heat
2a. BH3THF
2b. H2O2, NaOH

Cl

HO
HO

HO

OH

A)
B)
C)
D)
E)
Ans:

I
II
III
IV
V
C

OH

OH

OH

+
enantiomer

+
enantiomer

+
enantiomer

+
enantiomer

II

III

IV

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Moderate
111. What is the expected major product of the following reaction sequence?
Br

1. NaOEt, EtOH, 70 C
2a. O3, CH2Cl2, -78 C
2b. DMS

H
O

A)

OH

B)

OH
O

C)

O
O

CH

HC

D)

O
O

E)
Ans:

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Moderate
112. What is the expected major product for the following reaction?
1. OsO4, pyridine
2. H2O, NaHSO3

OH
+ enantiomer

A)

OH
OH
+ enantiomer

B)

OH
OH

+ enantiomer

C)

OH
H

O
+

D)

OH

OH
+ enantiomer

E)
Ans:

OH

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Moderate
113. What is the expected major product of the following reaction sequence?
1. t-BuOK
Cl
2. KMnO4, NaOH, cold

A)

OH

OH + CO2

B)

OH

C)

+ enantiomer

OH

OH

D)

+ enantiomer

OH
+ enantiomer

E)
Ans:

OH

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Moderate
114. What is the expected major product of the following reaction sequence?
1. t-BuOK, t-BuOH

Cl

2a. O3, CH2Cl2


2b. Me2S

+
H

A)

O
H

B)

OH
OH

C)
OH

D)

+ enantiomer

OH

O
H

E)
Ans:

H
O

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Hard
115. What is the expected major product of the following reaction sequence?
Cl

1. t-BuOK, t-BuOH
2. HBr

Br

Br

Br

Br

Cl

Br
I

A)
B)
C)
D)
E)
Ans:

II

III

IV

I
II
III
IV
V
C

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Hard
116. For the following reaction sequence, which molecule is an expected major product?
Br

1. t-BuOK
2a. OsO4, pyridine
2b. H2O, NaHSO3
OH
HO

A)
OH

B)

OH

OH

C)

OH

D)
Br

E)

OH

Ans: A
Topic: Synthetic Strategies
Section: 9.13
Difficulty Level: Hard
117. What is the expected major product of the following reaction sequence?
Br

1. NaOEt, EtOH, 70 C

2a. O3, CH2Cl2, -78 C


2b. DMS
O

A)

OH

B)

OH
O

C)

O
O

CH

HC

D)

O
O

E)
Ans:

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Hard
118. For the following reaction sequence identify the expected major organic products
and provide their stereochemical relationship.
Br

1. t-BuOK, t-BuOH
2a. BH3THF
2b. H2O2, NaOH

HO

HO

HO

OH

A)
B)
C)
D)
E)
Ans:

OH

II

I and II;
III and IV;
I and II;
II and III;
III and IV;
D

OH

III

enantiomers
enantiomers
diastereomers
diastereomers
diastereomers

HO
OH

IV

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Hard
119. For the following reaction sequence identify the total number, frequency and types
of stereoisomeric compounds expected as products.
1. NaOEt, HOEt, heat
Br

A)
B)
C)
D)
E)
Ans:

2a. Hg(OAc)2, CH3OH


2b. NaBH4, NaOH

2 total stereoisomers;
4 total stereoisomers;
4 total stereoisomers;
8 total stereoisomers;
8 total stereoisomers;
E

1 set of enantiomers
2 sets of enantiomers
4 diastereoisomers
4 sets of enantiomers
8 diastereomers

Short Answer Questions:


Topic: Introduction to Addition Reactions
Section: 9.1
Difficulty Level: Easy
120. bonds are quite susceptible to reaction with electron-seeking reagents, also
referred to as ____________________.
Ans:
electrophiles
Topic: Regioselectivity
Section: 9.3
Difficulty Level: Easy
121. The rule that correctly predicts the regiochemistry of most ionic additions to
alkenes is called ____________________.
Ans:
Markovnikov's Rule
Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
122. For the following reaction sequence provide the expected major organic product(s).
Include all stereoisomers showing relevant stereochemistry.
HI

Ans:
I

Topic: Hydrohalogenation
Section: 9.3
Difficulty Level: Easy
123. Provide the structure(s) of the expected major organic product(s) generated upon
completion of the following reaction scheme:
(CH3)2CHCH2CH CH2

Ans:

Br

HBr
ROOR

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate
124. The reaction of HCl with 2-ethyl-1-pentene or HCl with 3-methyl-2-hexene results
in the identical major product of 3-chloro-3-methylhexane. Provide a mechanistic
scheme showing the reaction of each alkene with HCl, including the intermediate
and product. Provide a brief explanation how the different alkene reactants were
transformed into the same product.
Ans:
H Cl

Cl

Cl
H Cl

most stable
carbocation

Electrophilic addition of a proton in the reaction between HCl and both alkenes
will result in formation of the most stable intermediate carbocation. Addition of
Cl to the tertiary carbocation formed in both cases results in the observed
product. The reason for the identical major product is a consequence of
regioselective addition to the double bond forming the same tertiary carbocation
intermediate.
Topic: Hydrohalogenation and Carbocation Rearrangements
Section: 9.3
Difficulty Level: Moderate
125. When the two constitutional isomers, 3,3-dimethyl-1-butene and 2,3-dimethyl-2butene, are reacted with HCl the same major product is formed. Provide a
mechanistic explanation for the observation.
Ans:
HCl
Cl

3,3-dimethyl-1-butene

Cl

HCl
2-chloro-2,3dimethylbutane
2,3-dimethyl-2-butene

most stable
carbocation

For the unsymmetrical 3,3-dimethyl-1-butene, the carbocation formed is 2, but


can readily undergo a methyl shift to form the more stable 3 carbocation, which
is the same as that formed from 2,3-dimethyl-2-butene. The addition of the
chloride ion to the carbocation forms the identical product, 2-chloro-2,3dimethylbutane.

Topic: Hydrohalogenation and Carbocation Rearrangements


Section: 9.3
Difficulty Level: Moderate
126. Addition of HI to the alkene of the cyclobutane in the scheme below, results in a
significant yield of the product shown. What other product(s) might also be
obtained? Explain with a mechanism and brief discussion the observation of the
given product as well as others that may arise.
HI

H+

fast

alternative 1
ring expansion

alternative 2

I
methyl shift

alternative 3

Ans:

1,2 addition

Regioselective addition of the proton of HI generates a secondary


carbocation. Rearrangement to a more stable 3o carbocation can occur by
two alternative pathways (1 and 2). Pathway 1 results in relief of ring
strain by expansion to a more stable 5-membered ring. The second
pathway involving a methyl shift is less likely; ring strain is not relieved
and becomes worse with incorporation of an sp2 carbon (bond angle 120)
into the cyclobutane (bond angle 90). The third pathway occurs if
addition of iodide to occurs before carbocation rearrangement. The first
pathway is most likely, resulting in the observed product.

Topic: Acid-Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy
127. For the following reaction sequence provide the expected major organic product(s).
Include all stereoisomers showing relevant stereochemistry.
H3O+

Ans:
OH
OH

Topic: Acid-Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy
128. For the following reaction sequence provide the expected major organic product(s).
Include all stereoisomers and clearly show relevant stereochemistry.
H3O+

Ans:
HO

OH

Topic: Acid Catalyzed Hydration


Section: 9.4
Difficulty Level: Easy
129. Provide the structure(s) of the expected major organic product(s) generated upon
completion of the following reaction scheme:
H3O+

Ans:
OH

OH

Enantiomers

Topic: Acid-Catalyzed Hydration


Section: 9.4
Difficulty Level: Moderate
130. The transformation shown below generates an achiral product from a chiral starting
material. Provide the structure of the expected product and a mechanism
explaining the transformation. Briefly explain why the product formed is achiral.
H

H 3O +

Ans:
OH

H+

H
O H

H
Hydride
shift

:B

O H
H

Upon addition of the proton to the alkene a 2 carbocation is formed that


undergoes a hydride shift to form a more stable 3 carbocation. The 3
carbocation is located in the center of the chain, and being sp2 hybridized
is planar. Addition of water to the central carbon produces a product with
no stereocenter and is thus achiral.
Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy
131. A reaction that could potentially yield two or more constitutional isomers, but as in
hydroboration-oxidation produces only one isomer, is said to be
_____________________.
Ans:

regioselective

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy
132. Any proper mechanism of hydroboration-oxidation must explain the observed
_________ addition of the H and OH to the alkene as well as the _____________
regiochemistry.
Ans:

syn, anti-Markovnikov

O H

Topic: Hydroboration-Oxidation
Section: 9.6
Difficulty Level: Easy
133. Provide the structure(s) of the expected major organic product(s) generated upon
completion of the following reaction scheme:
1. BH3THF
CH3CH2C(CH3)2CH CH2

Ans:

2. H2O2, NaOH

OH

Topic: Halohydrin Formation


Section: 9.8
Difficulty Level: Easy
134. Provide the expected major organic product from the reaction shown below.
Provide a brief explanation of any regioselectivity the reaction is expected to
produce.
Br2 / H2O

OH
Br

Ans:
The alcohol will be found at the tertiary carbon, being the more substituted
carbon. Initial formation of the bromonium ion will favor attack of the
water at the more substituted carbon which is more capable of stabilizing
the partial positive charge that develops in the transition state.
Topic: Halohydrin Formation
Section: 9.8
Difficulty Level: Moderate
135. For the following transformation below, provide a detailed step-wise mechanism
showing the electron flow using the curved arrow formalism.
Br

Br2

+ HBr

HO

Ans:
Br Br
HO

Br
HO

Br

Br
Br

O
H

+ HBr
O

Topic: Halohydrin Formation


Section: 9.8
Difficulty Level: Moderate
136. For the following reaction draw out the expected major organic product(s). Include
regiochemical and/or stereochemical details as relevant, and provide a short
justification for the product(s) drawn.
Br2, H2O

OH

OH
+

H
Br

Ans:

H
Br

The reaction takes place with Markovnikov regioselectivity and anti


stereospecificity, giving a racemic mixture of the halohydrin as the major
product.
Topic: Halogenation and Stereospecificity
Section: 9.8
Difficulty Level: Moderate
137. Draw Fischer projection formulas of the major product of the reaction between
(E)-2-methyl-3-hexene and aqueous Br2.
Ans:
Br2
H2O

HO
H

CH(CH3)2
H
Br
C2H5

H
Br

CH(CH3)2
OH
H
C2H5

H
HO

CH(CH3)2
Br
H
C2H5

Br
H

CH(CH3)2
H
OH
C2H5

The reaction takes place with anti stereospecificity. Since the alkene is
symmetrically substituted, Markovnikov rule is not applicable, and the
reaction is not regioselective. The product mixture would therefore consist
of 2 pairs of enantiomers, which are constitutional isomers of each other.

Topic: Oxidative Cleavage


Section: 9.11
Difficulty Level: Easy
138. Provide the structure(s) of the expected major organic product(s) generated upon
completion of the following reaction scheme:
1. O3

2. (CH3)2S, (DMS)

Ans:
H

O
O

and

Topic: Predicting Reaction Products: Halohydrin Formation and Stereospecificity


Section: 9.12
Difficulty Level: Moderate
139. Predict the structure(s) of the expected major organic product(s) of the following
reaction. Include regiochemical and/or stereochemical details as needed.
H

Br2

CH3OH

H
+

Ans:

Br

OCH3

Br

OCH3

The reaction takes place with Markovnikov regioselectivity and anti


stereospecificity. As the product is chiral, the products are diastereomers.
Topic: Predicting Reaction Products: syn Dihydroxylation
Section: 9.12
Difficulty Level: Moderate
140. Draw Fischer projection formula(s) of the major product(s) of the reaction between
(Z)-2-methyl-3-hexene and cold, alkaline KMnO4.
KMnO4
cold, dil

Ans:

CH(CH3)2
H
OH
H
OH
C2H5

CH(CH3)2
HO
H
HO
H
C 2H 5

The reaction takes place with syn stereospecificity, giving a racemic


mixture of the diol product.

Topic: Predicting Reaction Products: syn Dihydroxylation


Section: 9.12
Difficulty Level: Moderate
141. Draw Fischer projection formula(s) of the major product(s) of the reaction between
(Z)-3-methyl-3-hexene and catalytic OsO4 NMO.
CH2CH3
H 3C
OH
H
OH

OsO4
NMO

CH2CH3
HO
CH3
HO
H

C 2H 5

Ans:

C2H5

The reaction takes place with syn stereospecificity, giving a racemic


mixture of the diol product.
Topic: Predicting Reaction Products: anti Dihydroxylation
Section: 9.12
Difficulty Level: Moderate
142. Draw Fischer projection formula(s) of the major product(s) of the reaction between
(Z)-3-methyl-3-hexene and MCPBA, followed by acidic water.
CH2CH3
HO
CH3
H
OH

1) MCPBA
2) H3O+

CH2CH3
H3C
OH
HO
H

C 2H 5

Ans:

C2H5

The reaction takes place with anti stereospecificity, giving a racemic


mixture of the diol product.
Topic: Predicting Reaction Products: Oxidative Cleavage
Section: 9.12
Difficulty Level: Moderate
143. Predict the product(s) of the oxidation of 2,3,4-trimethyl-1,5-heptadiene upon
treatment with O3 followed by dimethylsulfide (DMS).
Ans:
1) O3
2) DMS

OH

O
OH

CO2

H2O

Topic: Synthetic Strategies


Section: 9.14
Difficulty Level: Moderate
144. A common problem in the acid catalyzed hydration of alkenes is the formation of
an ether byproduct. Explain the formation of the ether byproduct in relation to the
reaction below:
H3O+
H2O

OH

H+
O
OH

Ans:

Topic: Predicting Reaction Products: Halohydrin Formation and Stereospecificity


Section: 9.12
Difficulty Level: Hard
145. Identify the structure(s) of the expected major organic product(s) of the following
reaction. Draw the products in the expected chair conformations and include
regiochemical and/or stereochemical details as needed.
H

Br2

CH3OH

Ans:
H

Br
H

OCH3
CH3O H
Br

Br
Br

OCH3
H

H3CO
Br

OCH3

The reaction takes place with Markovnikov regioselectivity and anti


stereospecificity. The starting material is shown as a single enatiomers,
and thus produces two diastereomers. The product containing the cis
fused rings is capable of a ring flip.

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Hard
146. Starting with (2R,3R)-2-chloro-3,4-dimethylpentane, a) draw the expected major
product for each step, including regiochemical and stereochemical details when
needed. In addition, b) briefly explain the mechanistic rational for each
transformation.
i. t-BuOK/t-BuOH, heat
ii. MCPBA/CH2Cl2
iii. H3O+
Ans:
Cl

H 3C H

t-BuOK/t-BuOH

MCPBA

(E2: Hofmann elimination)

(2R,3R)-2-chloro-3,4dimethylpentane

H3C H

(R)-3,4-dimethylpent-1-ene

CH2Cl2
syn addition

O
+

H 3C H
(R)-2-((R)1,2-dimethylmethylpropyl)
oxirane

H 3C H
(S)-2-((R)1,2-dimethylmethylpropyl)
oxirane
H 3O +

HO H
HO
H3C H
(2S,3R)-3,4dimethylpentane-1,2-diol

OH

HO
H3C H
(2R,3R)-3,4dimethylpentane-1,2-diol

Hofmann elimination occurs upon heating with the bulky potassium tertbutoxide base, through an E2 elimination. Epoxidation with MCPBA is
stereospecific (syn), giving a racemic (R,R & S,R) epoxide. Ring opening
of the epoxide under acidic conditions is regio- and stereospecific.

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Hard
147. For the following transformation a) identify the starting material with correct
stereochemistry and b) provide a complete reaction mechanism, including
stereochemistry, to account for the product shown.
?

1) MCPBA
MeO

2) MeOH, [H2SO4]

OH

Ans:
H
O

O
O

Cl
O

H
O

H
O

H O
O S OH
O
H3C

OH

H3C O
H
B:

H
O
H3C O

MeO

Step 1

Step 1 involves the epoxidation of the (E) alkene by MCPBA, showing


only the enantiomer leading given product. Acid catalyzed ring opening
of the epoxide would occur with regiospecific addition of MeOH to the 3
carbon. Deprotonation by a general base (likely MeOH in this example)
provides the product, which upon bond rotation has the same
conformation as the product given in the question.

OH

Topic: Synthetic Strategies


Section: 9.13
Difficulty Level: Hard
148. Consider the information given below and identify the structure of the unknown
compound A, with a molecular formula of C8H14. Compound A reacts with
Br2/CCl4. Upon reaction with excess H2/Ni 1-ethyl-2-methylcyclopentane is
produced. Subjecting A to ozonolysis, the product shown below is produced as the
major organic product. Draw the correct structure of compound A, and provide a
brief and clear explanation relating the data provide with the structure selected.
O

Ans:

A must be 3-ethyl-4-methylcyclopentene.
explained as shown below:

This given data can be

C8H14
Reacts with Br2,CCl4:
A must contain a bond
H2, Ni

A must contain the


same carbon skeleton
as the product after
hydrogenation, and a
bond

ozonolysis
O
O

The location of the bond position in A is identified


from the structure of the ozonolysis product

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