Name ________________________________

2


1a. Rank the molecules below in order of decreasing pK
a
(increasing acidity) of the
indicated H: (2 points)


A
B C D
H
H
H
H



least acidic
most acidic
> pKa > >
C D A
B




1b. Rank the following in order of reactivity with Br
2
in the presence of FeBr
3
. (2 points)


S Br
O
A B C D





most reactive
least reactive
> > >
A
B
D
C



Name ________________________________
3


2a. Rank the following species by carbocation stability: (2 points)


A C B



least stable most stable
B A C




2b. Rank the following species by carbocation stability: (2 points)



H
3
C H
H
H
3
C CH
3
CH
3
H
3
C CH
3
OH
H
3
C CH
3
H
A B C D




least stable
most stable
A
D B C



Name ________________________________
4


3. Provide a mechanistic pathway for the biosynthesis of !-terpineol from geranyl
pyrophosphate. (5 points)

OPP
geranyl pyrophosphate
OPP
CH
2
CH
2
OPP
PPO
CH
2
internal
rotation
PPO
CH
2
CH
2
CH
2
OPP
OPP
geranyl pyrophosphate
!-terpineol
OH
!-terpineol
OH
H
2
O



Name ________________________________
5

4. Predict the products of the following Diels-Alder reactions. Show stereochemistry
when appropriate. (8 points)

O
O
H
H
H
O
H
H
C
H
O
H
N
O
O
O
O
C
N
H
H
Heat
Heat
Heat
Heat
a.
b.
c.
d.
~OR~


Name ________________________________
6



5. Over the arrows below, write in the reagents needed to produce the following
reactions in good yield. If more than one step is needed, number each step 1), 2), etc.
(6 points)


CH
3
H
H
3
C
H
HO OH
H
3
C
CH
3
H
H
CH
3
CH
2
C CCH
3
CH
3
CH
2
H
CH
3
H
O
O
H
3
C
H
3
C
O
H
3
C
H
3
C
O
OH
H
3
C CH
3
O
OH
H
3
C CH
3
1) OsO
4
2)NaHSO
3
H
2
Lindlar
mCPBA
H
2
SO
4
EtOH
NaOEt
a.
b.
c.
d.
e.