Chem 112A 2013

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Problem Set 3. Due 10/24/13 at the beginning of lecture.
You can also turn your problem set into your GSI anytime earlier than this either in person, or in
their mailbox on the 3
rd
floor of Latimer by the elevators.

Problems from Loudon:
Chapter 6: 32, 36, 39, 42-48, 50; Chapter 7: 25, 31, 53, 55; Chapter 5: 34, 35, 48a,
48b, 48d

Additional Assigned Problems:

1. Draw the products of the following reactions, include all stereoisomers that form as major
products.
a.


b. Draw two stereoisomers


c.


d. Draw one stereoisomer product:

Cl
2
H
2
O
1. Hg(OAc)
2
, CH
3
OH
2. NaBH
4
HBr
O
OH
H
2
Pd/C
Chem 112A 2013
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2. Draw the mechanism for the following reaction using arrows to show the flow of electrons.
(NaHCO
3
acts as a base in this reaction.) Show the formation of both stereoisomers in your
mechanism.


















3. The following reaction forms two stereoisomeric products. Based on the mechanism you drew
in problem 1, predict the products of the following reaction. Draw a mechanism to form these
products using arrows to indicate the flow of electrons. Show the formation of both
stereoisomers in your mechanism.




















OH
O
I
O
I
+
I
2
, NaHCO
3
CH
3
CN
OH
I
2
, NaHCO
3
CH
3
CN
Chem 112A 2013
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4. Draw the mechanism for the reaction that forms the product shown using arrows to show the
flow of electrons. (NaHCO
3
acts as a base in this reaction.)




















5. Draw the mechanism for the reaction that forms the product shown using arrows to show the
flow of electrons.














CO
2
H
Br
2
, NaHCO
3
CH
3
CN
Br
O
O
O
O
O
H
OH
1. Hg(OAc)
2
, THF
2. NaBH
4
, H
2
O
O
O
O
H
O
MeO
MeO
Chem 112A 2013
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6. Draw all possible stereoisomers of the following molecule. Note that the nitrogens in this
molecule are sp
2
hybridized. Assign R and S configuration to each asymmetric carbon. Label
any meso isomers.










7. Fill in the reagents in the boxes below.




N
N O
O
OH
OH
OH
OH
+
Chem 112A 2013
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8. Circle chiral or achiral for the following molecules:



9. Are the following molecules constitutional isomers, diastereomers, enantiomers, identical, or
different molecules?










Cl
Cl
Cl
Cl
Cl
Cl
chiral
achiral
chiral
achiral
chiral
achiral
Cl
Br
Br
Cl
COOH
Me
chiral
achiral
chiral
achiral
chiral
achiral
chiral
achiral
chiral
achiral
O
H
H
H
H
O
Cl
H
O
H
Cl
HO
H
HO
H
different compounds
identical
constitutional isomers
diastereomers
enantiomers
different compounds
identical
constitutional isomers
diastereomers
enantiomers
different compounds
identical
constitutional isomers
diastereomers
enantiomers
different compounds
identical
constitutional isomers
diastereomers
enantiomers
Chem 112A 2013
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10. The structure of quinine, an antimalarial drug, is shown below:


a. Draw a diastereomer of quinine.












b. If [!] of quinine is -165, calculate the %ee of a solution with the following [!] values: -30, +82.








c. If a solution contains 60% quinine and 40% of its enantiomer, what is the %ee of the solution?





d. What is [!] for the solution described in part c?








N
HO
H
N
H
H
3
CO
Chem 112A 2013
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11. S-adenosylmethionine (SAM) is shown below. SAM is an important methylating agent in
biological systems. One stereoisomer of SAM is made biochemically, and its structure is shown
below. Note that the absolute configuration of sulfur is shown.


a. If the lone pair has the lowest priority, assign the absolute configuration at sulfur.


b. Do you think that the sulfur stereocenter will racemize readily at room temperature? Explain
your answer.


N
N
N
N
NH
2
O
OH OH
H H
H H
S
HOOC
H NH
2