Chem 331 key

Name ___________________
Exam #2
Friday, October 19, 2007

This is an open-book, open notes exam. Please show your work in detail.

1. (20 points) Draw the structures of B and C, and give IUPAC names for A, B, and C. You do not have to
show mechanisms, but you do need to show stereochemistry clearly.

PBr3 B Mg;
C
OH C7H13Br CH3CN C9H16O
A
(1S, 3S)-3-methylcyclohexanol

Br
O
(1R, 3S)-1-bromo-3-methylcyclohexane
1-((1R, 3S)-3-methylcyclohexyl)ethanone

2. (20 points) Indicate the expected major product. Explain your reasoning in detail.
O
Br
1. ONa
O O
Br 2. KOH
O
benzylic Br more reactive
O
HO O O O
O

Br
O O

O
inverted O O
Br
O
same
inverted
3. (20 points) Outline the synthesis steps to convert D into E. In addition to D, you may use any piece
that contributes three or fewer carbons to the final product.

HO
CrO3
D
O
TsCl, pyridine
MgCl

MCPBA CH3MgBr
TsO
O OH

4. (20 points) Deduce the stucture of F, and draw an arrow-pushing mechanism for the transformation.

H+
13C NMR 1H
O NMR
H+ F
14.6, q 1.42, d, J = 7.3 Hz, 3H
C9H10O 53.0, d 3.63, dq, J = 4.2, 7.3 Hz, 1H
127.5, d 7.22, dd, J = 8.1, 2.4 Hz, 2H
128.3, d (2) 7.31, dd, J = 8.1, 8.2 Hz, 2H
H 129.0, d (2) 7.38, td, J = 8.2, 2.4 Hz, 1 H
O 137.8, s 9.65, d, J = 4.2 Hz, 1H
CH3 200.8, d

OH H3C H3C
H H H
CH3 O O
H
F
5. (20 points) Draw a detailed arrow-pushing mechanism for the following transformation. 5/20 points
for correctly showing the mapping of the starting material onto the product.

b bb bf
c a b
a
S c
d CO2CH3 + f e O-e a-f
O f e-f
O eO O d CO2CH3 a-d
O-f
O f-H
f-S d-H
S +
f
O S

O
DMSO
CO2CH3
O O
O S

O CO2CH3
CO2CH3
O
O O O S
S
O

CO2CH3 H+ CO2CH3
O O
O O
transfer
S S

O O