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KEY - Chem 14D Final Exam Review Packet – P.1
Garg, Spring 2010
1. Draw the major product for each of the following reactions. Where applicable, answers without relative stereochemistry will be given zero credit. a. Me Et Me Et
H2, Pd/C
b.
O3
DMSO
O
c.
heat+
CO2Me
CO2Me
CO2Me
CO2Me d.
HgSO4
H2SO4, H2O
O
e.
O OMeMeO
H+
MeOH (excess)
f.
OMe
O
OEt
O
H+
EtOH g.
OMe
O OH
MeMgBr
(2 equiv) h.
BrBr2
FeBr3
i.
fuming
sulfuric acid
OMe
Br
OMe
Br
SO3H
KEY - Chem 14D Final Exam Review Packet – P.2
Garg, Spring 2010
2. Provide the missing reagents for the transformations shown below. a.
OH OMe
1. NaH
2. MeI b.
t-BuOK
t-BuOH
Br c.
OHONaBH4
d.
OH
1. Hg(OAc)2, H2O
2. NaBH4 e.
O
H2NMe
H+
NMe
f.
CrO3
H+, H2O
O
g.
O
1. LDA
2. MeI
O
Me
h.
OHCrO3
H+, H2OOH
O
i.
PCl3
or SOCl2
OH
O
Cl
O
j. NH2 NO2
F3CCO3H
KEY - Chem 14D Final Exam Review Packet – P.3
Garg, Spring 2010
3. Provide a potential precursor to each of the following compounds (in other words, perform a single-step retrosynthesis). Also draw out the corresponding forward reaction with reagent that could be used to synthesize the given molecule. Note: In many cases, there is more than one correct solution a.
Br
Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
BrBr2
FeBr3
b. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
1. Mg
2. CO2
OH
O
Br
Br
OH
O
KEY - Chem 14D Final Exam Review Packet – P.4
Garg, Spring 2010
c. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
cat. H2SO4
benzene, heat
OH
OH
d. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
NaOH, H2O
heat
H
O
H
O
H
O+
H
O
H
O+
H
O
e. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
heat
CO2Me
CO2Me
CO2Me
CO2Me
+
CO2Me
CO2Me
+
CO2Me
CO2Me
KEY - Chem 14D Final Exam Review Packet – P.5
Garg, Spring 2010
f. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
H2, Pd/C
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
g. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
OH
Me
O
Me
O
Me
SEt
OH
Me
SEtNaSEt
h. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
1.Cy2BH
2. H2O2, NaOH
HH
O
H
H
O
KEY - Chem 14D Final Exam Review Packet – P.6
Garg, Spring 2010
i. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
HNMe2
heat
NMe2
O
OH
O
OH
O
NMe2
O
j. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
Br2
AcOH
O O
O O
Br
Br
k. Identify precursor(s):
Forward reaction (provide starting material and reaction conditions):
CrO3
H+, H2SO4
O
O
KEY - Chem 14D Final Exam Review Packet – P.7
Garg, Spring 2010
4. Provide detailed arrow-pushing mechanisms for the following transformations. a.
MeO
OO
MeO
O
AlCl3
O
Cl
b.
NO2HNO3
H2SO4
c.
OEt
O
OH
O
EtOH
H+, Heat d.
O
HNaOH, H2O
Heat
O
H
O
e.
OO
1. LDA
2.
Br f.
OH O
NaOH
H2O SEE NEXT FEW PAGES FOR MECHANISMS
KEY - Chem 14D Final Exam Review Packet – P.8
Garg, Spring 2010
5. Provide syntheses of the following target molecules. You may use common reagents, fragments of 2-carbons or less (these fragments may contain atoms other than just carbon, including hydrogen, oxygen, MgBr, and Li), and any of the compounds shown in the Chem 14D Toolbox. It is not necessary to show mechanisms or a retrosynthetic analysis in your solution.
Chem 14D Toolbox
H
O
Cl
O
OMe
Br
O
H
a.
O
OMe
OH b.
H
O
Br c.
NMe
d.
O
OH
(ibuprofen)
KEY - Chem 14D Final Exam Review Packet – P.9
Garg, Spring 2010
5a. Retrosynthesis (not required):
O
OMe
OH
O
OMe
O
O
OMe
O
OH
MgBrBr
Forward synthesis:
BrBr2
FeBr3
1. Mg
2. CO2
O
OHH+, MeOH
heat
O
OMeAlCl3
O
Cl
O
OMe
O
NaBH4
O
OMe
OH 5b. Retrosynthesis (not required):
Forward synthesis:
H
O
Br
H
O
H
O
H
O
+
O
H
O
H
+
O
H
O
H
+NaOH, H2O
heat
H
O
heat
H
O
H
O
H
O
Br
H2, Pd/C Br2
FeBr3
KEY - Chem 14D Final Exam Review Packet – P.10
Garg, Spring 2010
5c. Retrosynthesis (not required):
Forward synthesis:
NMe
O O
NMe
OO
O O
O
Cl
AlCl3 1. LDA
2. MeI
1. LDA
2. MeI
1. LDA
2. MeI
H+
H2NMe
5d.
Retrosynthesis (not required):
Forward synthesis:
O
OHBr OH
Br
O
AlCl3
O
Cl
O
1. LDA
2. MeIO
1. LDA
2. MeIO
Zn(Hg)
HCl, heat
Br2
FeBr3
Br
1. Mg
2.
OH
H
O
PBr3
BrO
OH
1. Mg
2. CO2
KEY - Chem 14D Final Exam Review Packet – P.11
Garg, Spring 2010
5d. ALTERNATE SOLUTION
Retrosynthesis (not required):
Forward synthesis:
O
OH
O
Cl
O
O
OH
OH
OH
(See solution above)
O
AlCl3 MeMgBr
OH
cat. H2SO4
benzene, heat
1. BH3
2. H2O2, NaOH
OH
CrO3
H+, H2O
(See solution above)
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