Chem 332
Exam 4
May 30, 2003
Prof. Fox
180 minutes
250 points
The exam is open book,
Open notes. Models are permitted
Show your work in detail
WRITE YOUR NAME ON EVERY PAGE
NAME
Chem 332, Exam 4. March 30, 2003
NAME
1. Circle the correct product (no mechanisms or partial credit). 8 pts
OH
O
O
MnO2
OH
O
OH
O
OH
OH
O
2. Circle the correct product (no mechanisms or partial credit). 10 pts
H
Me2N
Δ
Me2N
H
H
O
Me2 N
H
+
H
H
O
Me2 N
H
O
Me2N
H
H
H
O
H
H
O
Me2N
H
O
Me2N
H
O
Me2N
H
Me2N
O
H
O
Chem 332, Exam 4. March 30, 2003
NAME
3. Circle the correct product (no mechanisms or partial credit). 10 pts
O
Et
Me
Et
MeOH, H+
HO
Et
HO
Et
Et
Me
OMe
Et
Me
OMe
HO
Et
HO
Et
Me
MeO
Et
Me
MeO
Me
Et
OMe
Et
OH
Et
OH
Me
MeO
Et
MeO
Me
Et
OMe
Et
4. Circle the aromatic molecules. No partial credit. 12 pts
CH3
N
N
Et
N
Me
OH
Et
Et
OH
Chem 332, Exam 4. March 30, 2003
5.
NAME
It is expected that the treatment of iodonium salt A with pyridine would give a single product.
Circle the correct product, and provide a detailed explanation for the stereochemical outcome.
Your answer should include well drawn 3-dimensional representation of the trans-decalin framework.
H
O
CO2H
I–
H
I+
pyridine
H
CO2H
A
H
O
O
H
I
CO2 H
H
O
H
I
I
CO2H
CO 2H
H
O
H
CO2H
I
H
O
O
O
30 pts
Chem 332, Exam 4. March 30, 2003
6.
NAME
Provide a detailed mechanism for the thermal reaction shown below. Use your knowledge
of molecular orbital theory to explain the stereochemical outcome.
+
CH3
H3C
O
CH3
O
O
Δ
H O
O
H3C
H O
30 pts
Chem 332, Exam 4. March 30, 2003
7.
NAME
Provide a synthesis of C, using B as a starting material. Additionally, you may use benzene and
any other materials that contain four carbons or less.
Ph
Ph
35 pts
OMe
B
C
Chem 332, Exam 4. March 30, 2003
8.
NAME
Provide a detailed arrow pushing mechanism.
H
H+
MeO
MeO
HO
H
H
30 pts
Chem 332, Exam 4. March 30, 2003
NAME
9. D-(+)-altrose is oxidized by HNO3 to give an optically active diacid.
Circle the naturally occuring D-aldohexose that would give that same diacid upon HNO3 oxidation.
25 pts
10.
Identify the following pairs as identical, anomers, enantiomers, or
(non-anomeric) diastereomers. Write your answers on the line below the structures.
OH
H
H OH
O
H
H
HO
OH
OH
OH
OH
H
HO
H
H
OH
HO
HO
O
O
O
H
H
OH
OH
H
H
HO
H
OH
CHO
OH
OH
H
OH
CH2OH
H
H
HO
H
CH2OH
OH
OH
H
OH
CHO
OH
OH
OH
OH
10 pts for each
Chem 332, Exam 4. March 30, 2003
NAME
11. Provide a multistep synthesis of E using D, phenylalanine, and any other materials. (30 points)
CH3 O
O
O
N
H
CH3 O
H
N
O
O
D
O
O
E
N
H
NH2
= polystyrene