CHEM282 Chem281 Review sheet

Dr. Uwe Kreis, SFU Pg - 5 -

CHEM 281 Review - Answer Sheet
C Indicate whether the following pairs of compounds are identical or are enantiomers,
diastereomers, or are constitutional isomers. Provide the systematic name for the
FIRST compound of each pair.
Me
I
Me
I
Me
Me
Cl Cl Cl Cl
O H OH O H OH
and
a)
b)
c) and
d)
and
and
name:
name:
name: name:
relationship:
relationship:
relationship:
relationship:
Diastereomers
Identical
Diastereomers Enantiomers
(2R,4R)-2,4-dichloropentane
(1R,3S)-1,3-cyclopentadiol
(1R,2S,4S)-1-iodo-4-isopropyl-
2-methyl-cyclohexane
(3R)-1,3-dimethyl-1-cyclohexene

C For each of the following reactions provide the product and name it, identify the
mechanism, and suggest what happens to the reaction speed if the concentration of
starting material is doubled, if the concentration of alcoholate is doubled.
Br
Cl
Cl O K
+
OMe
OMe
O
+
KOMe
a)
b)
+
KOMe
c)
+
S
N
1
3-methoxy-3-methylpentane
S
N
2
1-methoxy-3,4-dimethylpentane
S
N
1/S
N
2
diisopropyl ether

a) This is a tertiary halide and the substitution will follow an S
N
1 mechanism. As a first
order reaction, this is dependent on the substrate concentration but not the nucleophile
concentration. Doubling the substrate concentration will double the speed of the
reaction, doubling the nucleophile concentration will not change the speed.
CHEM282 Chem281 Review sheet
Dr. Uwe Kreis, SFU Pg - 6 -
b) This is a primary halide and follows an S
N
2 mechanism. As a second order reaction, it
is dependent upon the concentration of both the substrate and the nucleophile.
Doubling the concentration of either will double the reaction speed.
c) A secondary halide could follow either mechanism. Based on the reaction conditions,
one usually predominates. One way to measure that is to compare reaction speeds
based on nucleophile concentrations. Doubling the amount of substrate or nucleophile
will increase the speed of the reaction. Increasing substrate concentration will speed it
up more.
C Please give the product(s) of the following reactions and identify the reaction
mechanism(s):
A)
OTs
O Na
+
O
+
S
N
2 & E2

B)
Cl
OH
NaOH
+
E1 (E2) & S
N
1

C)
OH
H
2
SO
4
heat
E1

D)
O
I
OH
HI
heat
S
N
2

CHEM282 Chem281 Review sheet
Dr. Uwe Kreis, SFU Pg - 7 -
C Deduce the identity of the compound from the data provided.
C
10
H
14
O: IR (cm
-1
):
3200-3500 (broad) = O-H stretch
3050 = C(sp2)-H str. , 2950 = C(sp3)-H str.
1610 = C=C str. aromatic
1
H NMR(): 1.0 (s, 6H) = 2 identical CH3 groups, no neighbors
2.0 (s, 3H) = 1 CH3 group, next to slightly deshielding group
2.8 (broad s, 1H) = OH signal, aliphatic alcohol
7.3 (d, 2H), 7.6 (d, 2H) = aromatic protons, 4H total = disubstituted, d & d = para

C Draw the following molecules:
a) (2R,3R)-3-ethyl-5-methyl-2-hexanol
b) trans-1-chloro-3-ethoxy-cylcohexane
c) 4-ethyl-3,3-dimethyl-hexanoic acid
d) (3R,4S)-4-hydroxy-3-methylcyclohexan-1-one
Complete the following reaction schemes (please indicate where racemic mixtures will
be formed in that case you only need to draw one stereoisomer):
a)
O
OH
OEt
PhCO
3
H
NaOEt
EtOH
S
N
2 reaction of
EtO
-
nucleophile
at sterically less
hindered position
racemic
racemic

b)
OH
OH
OH
OH
OsO
4
please draw all stereoisomers obtained and indicate their relationship
+
diastereomers
(syn addition)

OH
Et
H
H
Cl
OEt
O
H
H
Me
OH
O
OH
CHEM282 Chem281 Review sheet
Dr. Uwe Kreis, SFU Pg - 8 -
c)
OH
BH
2
OH
H
2
SO
4
heat
BH
3
THF
H
2
O
2
NaOH

d)
OH
H
2
SO
4
heat

e)
H
2
, Pd/C
indicate
stereochemistry

C Propose a mechanism for the following reaction.
O
Br
O
OMe
C H
3
O
C H
3
O Br
O
NaOMe
step A
step B

A small amount of a product containing a six membered ring is also formed. Give the
structure for that product and explain how it is formed and why so little of it is formed.
O
Br
C H
3
O
O Br
O
CH
3
O
O
C H
3
NaOMe
step C
step D

The nucleophile (methoxide) will attack the least hindered carbon of the epoxide to open up the oxiran ring in
an S
N
2 mechanism (step A). This creates an alcoholate intermediate which can do a backside attack on the
primary carbon carrying the bromine substituent, which forms the 5-membered ring ether (step B).
To form the six membered ring side product, the methoxide attacks at the sterically more hindered secondary
position of the oxiran ring (step C) which will close in the same way by intramolecular substitution of the
bromine to form a six membered ring ether (step D). As the attack of the methoxide on the oxiran is an S
N
2
mechanism, it is governed by steric hindrance. The primary position reacts faster than the secondary position
which is why so little of the six-membered ring product is observed.
CHEM282 Chem281 Review sheet
Dr. Uwe Kreis, SFU Pg - 9 -
Draw in detail the mechanism of the following E2 elimination reaction. Give the
product and, referring to the mechanism, explain why that product is formed.
Cl
Me
Me
Cl
H
Me
Cl
Et O
Me
Me
NaOEt
EtOH
?
E2 requires anti alignment with axial leaving group, so the ring has to flip and
only C3 carries an H in anti position to allow elimination

Draw all stereoisomers of 1-hydroxy-N-methyl-1-phenyl-2-propanamine in perspective
formula. Label the configuration (R,S) on each. Please label the naturally occurring
(1R,2S) isomer which is called ephedrine (used to treat asthma).
H
H
O H
NHMe
O H
NHMe
H
H
H
NHMe
O H
H
O H
H
H
NHMe
R
S
R
S
R
S
R
S
<enantiomers>
<enantiomers>
ephedrine

CHEM282 Chem281 Review sheet
Dr. Uwe Kreis, SFU Pg - 10 -
1 Give all possible products of the following reactions. For (b) indicate the stereo-
chemistry of the product and name it. Indicate the mechanism(s) for (d).
OH
Cl
Cl
OTs
Br
I
Cl
OH
OEt
OEt
OH
OH
OH
Cl
a)
b)
c)
d)
H
2
SO
4
heat
NaI
acetone
Cl
2
H
2
O
NaOEt
EtOH
e)
NaOEt
EtOH
f)
H
2
O
NaOH
+
S
N
2 mechanism
inversion of configuration
(1S)-1-cyclopentyl-1-iodoethane
+
+
+
Strong base - E2/S
N
2

Br OEt
g)
EtOH
+