2012 Practice Exam 2-B

8:10 — 9:20 a.m.

Name:

Section TF:

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. ____________ / 14
________________ / 100
5. ____________ / 16

6. ____________ / 12

7. ____________ / 12

8. ____________ / 10
 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)!

Cl
1. Cl
a)

2.

3.

Br 1.
b)
2.

3.

OH 1. OH
c)
2.

3.

D D D
1.
d) +
2.
OTs OMe OMe
3.

_______ / 12
 2 Name:

2. Fill in each box with the starting material or 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.

CO2H Br2
a)
HO2C

1. HBr, ROOR
b)
2. NaSH

CN
1. PBr3
c)
2. NaCN
H3C

OH
Ph Et
1. BH3, THF
d)
2. H2O2, NaOH Me H
H
(as a racemic
mixture)

_______ / 12
 3 Name:

3. Consider the structure and properties of the amino acid L-threonine:

O OH
Melting point: 256 C

HO
Specific rotation: -27.4
NH2
a) Circle all stereogenic carbons in the structure above, and label each with R or S designation as
appropriate.

b) In the box below, draw the structure of the enantiomer of L-threonine.

c) In the box below, write the specific rotation of the molecule you drew in part (b).

d) In the box below, draw the structure of a diastereomer of L-threonine.

e) True or false (circle one): the melting point of the molecule you drew in part (d) as a diastereomer of L-threonine
must be 256 C.

TRUE FALSE

_______ / 12
 4 Name:

4. Consider the following molecule: CH3

H3C
H3C
CH3 Br
a) This molecule is expected to have two possible "chair" conformations. Draw clear representations of the
two different conformations in the boxes below.
A B

b) Circle the letter of the box containing the more stable conformer you drew above.

A B

c) This molecule is found to react slowly with potassium tert-butoxide to form a single product. Draw this product
in the box below. You do not have to draw the product in a chair conformation.

CH3

KOtBu

H3C t
BuOH
H3C
CH3 Br

d) In the space provided below, brief ly explain why the reaction above is so slow. Your explanation may refer to the
conformational isomers you drew above.

_______ / 14
 5 Name:

5. The sulfonate ester below undergoes solvolysis quite readily in water to form Alcohol A.

H2O

TsO HO
Alcohol A

a) Provide a complete curved-arrow mechanism for this transformation.

b) For each of the pairs below, circle the set of conditions that would favor SN2 mechanisms. Note that this question
is NOT related to part (a) above!

Substrate structure: Nucleophile:

OR NaCN OR CH3OH
Br
Br

Solvent: Concentration of nucleophile:

Acetone OR Water High OR Low

_______ / 16
 6 Name:

6. Alcohols can be converted to the corresponding alkyl fluorides by treatment with the reagent DAST, as
shown in the reaction below. This reaction proceeds analogously to treatment with phosphorus tribromide.

F HO
OH + S NEt2 F + S NEt2
F F
F F
alkyl
DAST fluoride
a) Provide a complete curved-arrow mechanism for this transformation and, for each step, identify 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.)

b) Using your knowledge of the mechanism, draw the product of the following reaction in the box provided. You
must indicate stereochemistry for full credit.

OH
DAST

_______ / 12
 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. (You may ignore stereochemistry.)

Starting Material:

OH

Desired Product

_______ / 12
 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
three or fewer total steps.

Starting Material:

OMe

SMe

(+/-)

Desired Product

_______ / 10
SCRATCH PAPER ONLY - NOTHING ON THIS SHEET WILL BE GRADED