You should allow yourself exactly three hours

to take this exam.

Last Name:

SOLUTIONS

First Name:
Section TF:
Important Notes:
1. This exam consists of 16 problems on 16 pages, plus this cover sheet, and two pages for scratch work
at the end of the exam.
2. All answers must be written in the spaces provided. Do not write anything in red ink. Answers
written on the back of a page will not be graded. Anything written on the scratch page will not be graded.
3. You are allowed to use a set of molecular models for this exam.

Name:

1. Each of the following transformations can be carried out in three or fewer steps. Fill in the reagents
required for each step. If a step is not needed, please put an "X" next to that number. Be sure to consider the
stereochemistry (if relevant)!
Mg0, Et2O
or
1. Li (2 equiv.)

a)
Br

NaSH

2. H2O
3.

Raney Ni
X

also: 1. KOt Bu, t BuOH

2. H 2, Pd/ C

MgBr
O

1.

b)

2. H+ workup
3. CrO3

Cl

c)

1. MeOH,
2. X
3. X

OMe

(+/-)

CN

1. NBS, CCl4
d)
2. NaCN
3.

(+/-)

Name:

1. Each of the following transformations can be carried out in three or fewer steps. Fill in the reagents
required for each step. If a step is not needed, please put an "X" next to that number. Be sure to consider the
stereochemistry (if relevant)!

a)

CH3

1.

Na0, NH3
CH3

2. CH2I2, Zn/Cu
(+/-)
3. X

conc.
H
1. 2SO4

b)

2. Br2

HBr

H3O+

KOtBu,
t
BuOH

conc.
H2SO4

3. X

c)

Br2

Br

Br

Br2

1.

HO
HO

2. OsO4
O

3. NaHSO4, H2O

O
O

1. NBS, CCl4
d)

2. KOtBu, tBuOH
3. mCPBA

(+/-)

Name:

3. Fill in each box with the major organic product of the indicated transformation. Be sure to give the
stereochemistry of each if it is relevant (e.g., whether it is racemic / single enantiomer)! Any chiral starting
materials are pure, single enantiomers unless otherwise specified.

OH

a)

1. SOCl2, pyridine
2. KI

KOtBu
b)
OTs

BuOH

D2O
c)

OD
D

cat. D2SO4
50 C

D2O

d)
cat. D2SO4
78 C

OD

(+/-)

Name:

4. Fill in each box with the starting material of the indicated transformation. Be sure to give the
stereochemistry of each if it is relevant (e.g., whether it is racemic / single enantiomer)! Any chiral products
are pure, single enantiomers unless otherwise specified.

CH2CH3

1. BH3, THF

a)

2. NaOH, H2O2

OH

H3C
CH3

1. NaNH2, NH3

b)

H3C

2.
3. Na0, NH3

Br

O
O

(1 equiv.)

c)

OH
HO

conc. H2SO4

d)

or
HO

Name:

5. Consider the alkene below.

a. Provide the best possible systematic name for this alkene in the box below. You may ignore R/S
designations.
(E)-4-isopropyl-5,6,6-trimethyl-3-heptene

b. In the box below, provide the best possible systematic name of a compound that would be a
diastereomer of the alkene shown above. You may ignore R/S designations.

(Z)-4-isopropyl-5,6,6-trimethyl-3-heptene

c. Assign R/ S configurations or hybridizations, as appropriate, to each of the atoms circled in the molecule
below.
(circle one)
H3C

sp

sp2

sp3

N
O

(circle one)
R
S

H
OH

(circle one)
R
S

(circle one)
sp

sp

Ph
3

sp

6
6.

Name:

Carefully consider the structures of each of the compounds depicted below.

(a) Draw this compound in its most stable conformation.

OH
OH

(b) Draw this compound in its most stable conformation.

(c) Draw this compound using a clear 3-D representation.

O
CH3
CH3

O
O
O

Name:

7. Consider the following synthetic transformation:

H

OH

Two E-2a students proposed different synthetic routes to the indicated product:
Barney suggested: 1. TsCl, pyridine; 2. KOtBu, tBuOH
1. SOCl2, pyridine; 2. KOtBu, tBuOH

Phil suggested:

a. Only one of these proposals gave the desired product. Which student was successful?

(circle one)
Barney

Phil

b. Briefly explain why only that synthetic route worked. Your explanation must include both chair
conformation drawings and "cartoon" orbital sketches for full credit. You do not need to draw any curvedarrow mechanisms.
Barney: TsCl gives a leaving group with retention of stereochemistry, which allows the ideal
orbital overlap f or an E2 elimination.
H

OTs

OTs

*CO OTs

CH

Phil: SOCl 2, pyridine gives a leaving group with inversion of stereochemistry, and thus it cannot
possess any antiperiplanar orbital overlap!
H
Cl

H
Cl

No periplanar orbitals!

Name:

8a. Provide a complete curved-arrow mechanism for the following transformation.

O

O2N

NO2

NO2

+ CO2

O
NO2

NO2

NO2

NO2
NO2

b. For the molecules shown below, draw a "cartoon" orbital sketch of the indicated frontier molecular
orbitals (HOMO and LUMO) in the boxes provided.

For a
diene:
LUMO

HOMO

For a
dienophile:

LUMO

HOMO

Name:

9. In the presence of a secondary amine, the reagent N-iodosuccinimide (NIS), is observed to react with
alkenes as shown below:
O

HN(CH3)2
+

N(CH3)2

(as a racemic mixture)

N-iodosuccinimide
(NIS)
a. Provide a complete curved-arrow mechanism for this transformation and, for every step, identify all the
frontier molecular orbital (donor/acceptor) interactions involved. Note that you only need to name the
orbitals; you do not need to draw either energy-level diagrams or "cartoon" orbital sketches. Keep in mind
that this reaction is observed to be both stereospecific (giving only anti addition) and regiospecific (giving
only the product with the iodine on the secondary carbon); the mechanism you propose must be consistent
O
with these observations.
O

HN(CH3)2
I

N(CH3)2

:N

(+/-)

(+/-)

Donor: nN
Acceptor: *CI

Donor1: CC
Acceptor1: *NI
Donor2: nI
Acceptor2: *CC

Donor: nNAcceptor: *NH

Products

b. Based on your answer above, provide a complete curved-arrow mechanism for the following
transformation. You need not identify the frontier molecular orbital interactions for this part.
O

H
HO

N
I

O
O

HO
I
I

:N

H
O

10

Name:

10. The following transformation should look at least somewhat familiar to you.
O
OH
HO

O
CH3

Hg(OAc)2, H2SO4

a. Provide a complete curved-arrow mechanism for this transformation. You may invoke solvent ("Sol:") for
deprotonations where necessary.
OAc

HgOAc

Hg
Ph
H
Hg OAc
H

HO

HO

H+

:sol

OH

OAc

HgOAc

Ph

HgOAc

Ph

Ph
H

O
O

HO

HO

HO

H+

OH Ph
O
CH3 H

O
CH3

:sol

b. Draw the product of the following analogous reaction in the box below in its most stable conformation.
You do not need to draw a curved-arrow mechanism.

HO

OH

O
O

H3C

Hg(OAc)2, H2SO4

11

Name:

11. You have just synthesized a new compound, and the following spectroscopic data is obtained:
From the mass spectrum, you deduce that the molecular formula is: C15H24
The infrared spectrum is:
100

90

80

70
%
T
R
A
N
S
M
I
T
T
A
N
C
E

60

50

40

30

20

10

0
4000

3800

3600

3400

3200

3000

2800

2600

2400

2200

2000

1800

1600
WAVENUMBERS

From the infrared spectrum, circle the functional

groups that are definitely present:

O H/ N H

C O

C C

1400

1200

1000

800

600

450

From the infrared spectrum, circle the functional

groups that are definitely absent:

O H/ N H

C N/C C

C O

C N/ C C

C C

The proton NMR spectrum (with expansions) is:

6H

2.86

1.25

1H
1H
12

11

10

ppm
Draw your best choice for the structure of this molecule in the box below.

12

Name:

12. You have just synthesized a new compound, and the following spectroscopic data is obtained:
From the mass spectrum, you deduce that the molecular formula is: C6H11NO2
The infrared spectrum is:
100

90

80

70
%
T
R
A
N
S
M
I
T
T
A
N
C
E

60

50

40

30

20

10

0
4000

3800

3600

3400

3200

3000

2800

2600

2400

2200

2000

1800

1600
WAVENUMBERS

From the infrared spectrum, circle the functional

groups that are definitely present:

O H/ N H

C O

C C

1400

1200

1000

800

600

450

From the infrared spectrum, circle the functional

groups that are definitely absent:

O H/ N H

HC N/C C

C O

C N/ C C

C C

The proton NMR spectrum (with expansions) is:

6H

4.45

2.41

1.94

2H
1H
12

11

10

2H
4

ppm
Draw your best choice for the structure of this molecule in the box below.

OCH3
H3CO

CN

13

Name:

13. You have just synthesized a new compound, and the following spectroscopic data is obtained:
From the mass spectrum, you deduce that the molecular formula is: C4H6O2
The infrared spectrum is:
100

90

80

70
%
T
R
A
N
S
M
I
T
T
A
N
C
E

60

50

40

30

20

10

0
4000

3800

3600

3400

3200

3000

2800

2600

2400

2200

2000

1800

1600
WAVENUMBERS

From the infrared spectrum, circle the functional

groups that are definitely present:

O H/ N H

C O

C C

1400

1200

1000

800

600

450

From the infrared spectrum, circle the functional

groups that are definitely absent:

O H/ N H

HC N/C C

C O

C N/ C C

C C

The proton NMR spectrum (with expansions) is:

1H

2.5

4.2

2.3

1H
1H

12

11

10

ppm
Draw your best choice for the structure of this molecule in the box below.

O
O

14

Name:

14. Provide a complete synthesis of the following desired product from the indicated starting material,
cyclopropanol, plus any alkynes with four or fewer carbons. You may use any inorganic reagents you wish.
The correct answer will require six or fewer total steps.
Starting Materials:
1. NaNH2, NH3

H2

OH

2. Cmpd. A

cyclopropanol

Lindlar cat.

plus any hydrocarbons

with four or fewer carbons
H2
HC

CH

Lindlar cat.

H2C

CH2

HBr
Br

Compound A

Cl2,
OH

Cl
O

Desired Product
(as a racemic mixture)

15

Name:

15. Provide a complete synthesis of the following desired product from the indicated starting material, plus
any inorganic and organic reagents you wish, but all carbons from the starting material must end up in the
product. You may ignore stereochemistry. The best answer will require five or fewer total steps.
Starting Material:

OH

1. O3
2. Me2S

CHO

CHO

NaBH4
MeOH
OH

PBr3 (or other

leaving groups
are OK)

1. NaH (xs or 2 equiv.)

2. EtBr (xs or 2 equiv.)

Br

Br

NaOEt,
EtOH

OEt

EtO

Desired Product

16

Name:

16. Provide a complete synthesis of the following desired product from the indicated starting material,
fumaric acid. You may use any organic or inorganic reagents you wish. The correct answer will require three
or fewer total steps.
Starting Material:
O

CO2H
OH

HO
CO2H

fumaric acid

(+/-)

1. O3
2. H2O2

HO

O
O

HO
OH
O
O

OH

Desired Product
(as a racemic mixture)