Practice Final Exam A

8:30 — 11:30 a.m.

Name:

Important Notes:

1. This exam consists of 18 problems on 18 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 pages will not be graded.

3. You are allowed to use a set of molecuar models for this exam.

Problem Score Problem Score

1. ____________ / 16 10. ____________ / 18

2. ____________ / 16 11. ____________ / 18
3. ____________ / 16 12. ____________ / 18
4. ____________ / 16 13. ____________ / 18
5. ____________ / 18 14. ____________ / 18
6. 15.
____________ / 18 ____________ / 16
7. 16.
____________ / 18 ____________ / 16 Total Score:
8. 17.
____________ / 14 ____________ / 16
9. 18.
____________ / 14 ____________ / 16 ______________
/ 300
 1 Name:
1. Each of the following transformations can be carried out in no more than three steps. Fill in the reagents
required for each step. If a step is not needed, please put an "X" through that step.

1.
a)
OMe
2.

3.

O O
1.
b) NH2

2.

3.

1.
c)
2.

3.

O
1.
d)
HO OH
2.

3.

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 2 Name:
2. Each of the following transformations can be carried out in no more than three steps. Fill in the reagents
required for each step. If a step is not needed, please put an "X" through that step.

OH 1.
a)

2.

3.

1.
b) OH
N
2. H

3.

O O
1.
c)
2.

3.

O O O
1.
d) OEt
2.

3.

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 3 Name:
3. Fill in each box with the single major organic product of the indicated transformation. Be sure to indicate
stereochemistry where relevant!

Cl
a)
KOtBu

CH3 t
BuOH

b) h

O
1. NaOEt, EtOH
c) EtO O 2. H+ workup
SH
OEt 3. HS , H+
4. Raney Ni

d) 1. Na0, liquid NH3

2. Cl2, H2O

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 4 Name:
4. Fill in each box with the starting material of the indicated transformation. Be sure to indicate
stereochemistry if it is relevant! For full credit, all reagents must be used in a meaningful way.

Cl
Ph Cl
Cl2
a)
H CH3
CH3

(+/-)

O O
1. O3
b) +
2. H2O2 OH

CH3
1. DIBAL, 78 C N
c)
2. H+ workup H
3. CH3NH2, pH 5

CH3
1. BH3, THF
d) 2. NaOH, H2O2
OH
(+/-)

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 5 Name:

5. Consider the following reaction sequence, ozonolysis of an alkene followed by reductive workup:

O O O O
O3 (CH3)2S
O
rearrangement
O 2 +
cycloaddition O S
O H H3C CH3

a) Draw a complete Lewis structure of ozone, showing all formal charges and lone pairs. Then draw out all
the molecular orbitals of ozone, clearly indicating which is the HOMO and which is the LUMO.

b) Your classmate suggests that ozone would react with dienes in a similar cycloaddition, as shown below.
Provide a complete curved-arrow mechanism for this proposed reaction.

O O
O O O O

c) Using a frontier molecular orbital (FMO) argument, briefly explain why the reaction shown in part (b) would not be
expected to proceed as shown.

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 6 Name:

6. We continue our exploration of alkene ozonolysis followed by reduction. The key intermediate is the ozonide,
highlighted below.

O O O O
O3 (CH3)2S
O
rearrangement
O 2 +
cycloaddition O S
O dimethyl H H3C CH3
sulfide

ozonide

a) The rearrangement to the ozonide occurs in two mechanistic steps as shown below. Draw a complete curved-
arrow mechanism to account for this transformation, and fully classify any pericyclic reactions.

O O H O
H (rotate)
O O
H H O
O O O
O O
ozonide

b) Identify the LUMO of the ozonide and the HOMO of dimethyl sulfide in the boxes provided below.

Ozonide LUMO: Dimethyl sulfide HOMO:

c) Now draw a complete curved-arrow mechanism for the reduction of the ozonide with dimethyl sulfide.

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 7 Name:

7. Upon treatment with the nitrosonium cation, compound A is transformed into compound B via the diazonium
intermediate shown below.
CH3 CH3 CH3
NO
H2O
H3C CO2H H3C CO2H H3C CO2H
S H+ S S

NH2 N2 OH
Compound A Diazonium Compound B
intermediate

a) Circle all of the stereogenic carbons in compound A above, and label each with the correct R/S
designation.

b) Draw a curved-arrow mechanism to account for both steps of the transformation of Compound A into
Compound B. Your mechanism must account for the observed stereochemistry to get full credit!

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 8 Name:
8. You have just synthesized a new compound, and the following spectroscopic data are obtained:
• From the mass spectrum, you deduce that the molecular formula is: C4H7ClO2.
• The infrared spectrum is:

From the infrared spectrum, circle the functional From the infrared spectrum, circle the functional
groups that are definitely present: groups that are definitely absent:

O H C O C C C N O H C O C C C N

• The proton NMR spectrum is:

3H

3H

1H

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

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 9 Name:
9. You have just synthesized a new compound, and the following spectroscopic data are obtained:
• From the mass spectrum, you deduce that the molecular formula is: C10H14O.
• The infrared spectrum is:

From the infrared spectrum, circle the functional From the infrared spectrum, circle the functional
groups that are definitely present: groups that are definitely absent:

O H C O C C C N O H C O C C C N

• The proton NMR spectrum is:

9H

2H 2H
1H

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

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 10 Name:

10. Provide a complete curved-arrow mechanism for the following transformation, a variant of the classic
Beckmann rearrangement.
OH
N TsCl, pyr
H
N
H2O

O O O
You may represent TsCl as: S
Ar Cl

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 11 Name:

11. The following transformation occurs when the dichloro ether below is treated with benzene and aluminum
trichloride.
OMe
OMe

Cl Cl
Cl

AlCl3
Compound X
a) Provide a curved-arrow mechanism to account for the formation of Compound X as shown above.

b) Compound X reacts rapidly with water via an SN1-type reaction, as shown below. Provide a curved-arrow
mechanism for the reaction of Compound X to give the products shown. Be sure that your mechanism
illustrates why this SN1 reaction is so rapid!
OMe O

Cl H2O H + MeOH + HCl

Compound X

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 12 Name:

12. Provide a complete mechanism for the following multistep transformation. Use the curved-arrow
formalism for each step.
O
Br O
NaNH2
(3 equiv.) 1.
O
Br O +
Na C C O
liq. NH3 2. excess TFA
(dry H+)

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 13 Name:

13. Provide a complete curved-arrow mechanism for both steps of the following transformation.
O
O MeO O

1. NaOMe, MeOH O
+ O OMe +
Ph 2. H+ workup O MeO OMe
OMe O Ph CO2Me

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 14 Name:

14. Provide a complete curved-arrow mechanism for the following transformation. Please note that although
thiamine is used in this transformation, this process takes place in the lab. No enzymes are involved.

O O
NaOH, H2O
2 Ph
H R Ph
Ph
H
N OH

S
(thiamine)

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 15 Name:

15. Provide a multistep synthesis for the desired product from the indicated starting material, any inorganic
reagents, and any organic reagents containing only one carbon. The best answer will require nine or fewer
steps.
Starting material:

plus any organic reagents

containing one carbon

Desired product

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 16 Name:

16. Provide a multistep synthesis for the desired product from the indicated starting material. You may use
any inorganic or organic reagents, but all carbons from the starting material must end up in the product. The
best answer will require eight or fewer steps.
Starting material:
O

plus any organic compounds

containing three or fewer carbons

NH2

Desired product (+/–)

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 17 Name:

17. Provide a multistep synthesis for the desired product from the indicated starting material. You may use
any inorganic reagents and any organic compounds with two or fewer carbons. The best answer will require
six or fewer steps.
Starting material:

plus any organic compounds

with two or fewer carbons

(+/-)

Desired product

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 18 Name:

18. Provide a multistep synthesis for the desired product from the indicated starting material. You may use
any inorganic reagents and any organic compounds with four or fewer carbons. The best answer will require
five or fewer steps.
Starting material:

plus any organic compounds

with four or fewer carbons

O CN

CN

(+/-)

Desired product

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SCRATCH PAPER ONLY - NOTHING ON THIS SHEET WILL BE GRADED
SCRATCH PAPER ONLY - NOTHING ON THIS SHEET WILL BE GRADED