Name:

Important Notes:

1. This exam consists of 8 problems on 8 pages, plus this cover sheet, and one page 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.

Problem Score

1. ____________ / 12

2. ____________ / 12
Total Score:
3. ____________ / 12

4. ____________ / 12
________________ / 100
5. ____________ / 12

6. ____________ / 16

7. ____________ / 12

8. ____________ / 12
 1 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)!

OH CN
1.
a)

2.

3.

OH Br
1.
b)
2. OH

3. (+/–)

OH
1.
c) Br

2.

3.

OH

1.
d)
2.

3.

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 2 Name:

2. Fill in each box with the best starting material or single major organic product of the indicated
transformation. Be sure to provide stereochemistry if it is relevant! Any chiral starting materials or products
are given as pure, single enantiomers unless otherwise specified.

Me

Br KOtBu
a)
tBuOH
Me

Br

H2O
b)

H
Me Br
Br2
c)
Me Br
H
(+/–)

1. BH3, THF HO H
d)
2. H2O2, NaOH
Me H

_______ / 12
 3 Name:

3. For each of the following molecules:

a) Indicate if the molecule is chiral or achiral by circling the appropriate term.

b) For those molecules that are chiral, draw the structure of the enantiomer.

CH3 Cl
chiral
H3C CH3
achiral
CH3

H3C
OH chiral

achiral

Cl CH3 chiral

H3C Cl achiral

Br
chiral

Br achiral

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 4 Name:

4. Provide a complete curved-arrow mechanism for the following transformation, which yields a ketene
(ketone + alkene). Note that there is plenty of excess pyridine present which can act as a base.

O TsCl, pyridine
C
O
OH
Note: You may show the structure of TsCl as: ketene

O
R S O

Cl

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 5 Name:

5. The following two-part transformation yields an interesting functional group known as an episulfide:

S Cl Cl
Ph S NaNH2 Ph
S + S
part (a) part (b)
(Ph = phenyl = C6H5) S NH2
episulfide
S
(+/–) Ph (+/–)

a) Draw a complete curved-arrow mechanism for part (a) only. Make sure that your mechanism accounts for the
observed regiochemistry and stereochemistry of this step.

b) Draw a complete curved-arrow mechanism for part (b) only. For every step of your mechanism, identify all the
frontier molecular orbital (donor/acceptor) interactions involved. (You only need to name the orbitals, e.g., !*CO.
Neither "cartoon" orbital drawings nor energy-level diagrams are necessary.)

_______ / 12
 6 Name:

6. Consider the molecule shown at right, which

was observed as the intermediate in a version of
the synthetic transformation described in Cl
problem 5 on the previous page.

a) On the molecule, circle any stereogenic S

carbon atoms and indicate (R) or (S) for each.
S
Ph

b) This molecule is expected to have two possible "chair" conformations. Draw clear representations of the
two different conformations in the boxes below.
A B

c) Circle the letter of the box containing the A B

more stable conformer you drew above.

d) You prepare the following diastereomer of the compound shown above and treat it with NaNH2, just as you did in
part (b) of the mechanism from question 5 on the previous page. Under these conditions, which of the two
possible products shown below would you expect to predominate? No explanation is needed.

Cl NaNH2
S or
S
S
S
Ph S
Ph

Circle one: product 1 product 2

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 7 Name:

7. Provide a complete synthesis of the following desired product from the indicated starting material. You may
use any other reagents you wish. You do not need to show any mechanisms. The correct answer will require
three or fewer total steps.

Starting Material:

(+/-)

Desired Product

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 8 Name:

8. Provide a complete synthesis of the following desired product from the indicated starting material. You may
use any other reagents you wish. You do not need to show any mechanisms. The correct answer will require
five or fewer total steps.

Starting Material:

OH

Desired Product

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SCRATCH PAPER ONLY - NOTHING ON THIS SHEET WILL BE GRADED