Chem 201 Name:_________________________

Final Exam - Key

Clearly indicate stereochemistry unless otherwise indicated. You may use molecular models. If you get
stuck, try numbering atoms and/or working backwards. Remember, we reward partial credit. Good
luck!

1. (16 pts) Circle the side of the equilibrium that would be favored.
a.
O +O H
stabilized
H .. by
N+ N resonance

b.
OCH3 OCH3

O O strong C=O pi bond

c.
stabilized O O
by ..
resonance N
N

d.

strong O OH
C=O pi bond + +
NH2 NH

2. (10 pts) Estimate the equilibrium constant (within a factor of 10) for the following
reactions.
a.
pKa ~36 pKa ~20
Li H H
O O
+ N + N Keq ~ 10(20-36) = 10-16
H Li

b.
pKa ~16 pKa -7
H H
O O -O O+ Keq ~ 10(-7-16) = 10-23

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Chem 201 Name:_________________________

3. (15 pts) In the box provided, write the approximate free energy difference, in kcal/mol
between the species indicated.
a.
Br Br Br between
Keq 2300 diaxial !G° 4.6 kcal/mol
H Br &
H
H diequatorial
H
b.
between
O H2 A O B O A&B !G° 0 kcal/mol
chiral catalyst
OMe OMe OMe
MeOH
NHAc 23 °C, 12 h NHAc NHAc
99 : 1
between
transition state leading to A !G° 2.8 kcal/mol
&
transition state leading to B

4. (15 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.1
O
Cl
+ Cl N
OH CH2Cl2 O 87%
O 20 °C, 48 h
Answer:

Cl I
Cl would
.. accept...
Cl ..
OH + OH O O
Cl + H
Cl
:A-
+ Cl
OH

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Chem 201 Name:_________________________

5. (20 pts) Suggest a plausible arrow-pushing mechanism for the following acid-catalyzed
reaction.2
OH O
O SPh cat. p-TsOH
77%
C6H6 MeO
MeO 80 °C, 4 h PhS

Answer:
.. H A +
O O O
OH OH2
+
..
MeO S MeO S MeO S
Ph Ph Ph

O + O O

MeO S MeO MeO

.. + H
Ph S PhS
-A:
Ph
or... O

MeO +S
Ph

6. (20 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.
OMe cat. p-TsOH
HO O O
OH

Answer:
-A: OMe
H A +OMe H O OH
:OMe .. +
HO OH
A
H
H
..
OMe +OMe
O OH :O OH

+ : A-
+O :OH O O H O O

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Chem 201 Name:_________________________

7. (15 pts) Suggest a plausible arrow-pushing mechanism for the following Rubottom oxidation
reaction.3
OSiMe3 mCPBA O
OSiMe3 85%
Ph CH2Cl2 Ph
23 °C, 1 h

Answer:
A
R R H H
.. Me3Si :OH
O
.. O O O+
O O +O
O H +O
-
H Me3Si Me3Si ..
O .O
. Ph Ph Ph
O does not open
Me3Si
spontaneously
Ph (at -40 °C)

: A-
: A-
- + H + H Me3Si
Me3Si :OH Me3Si O Me3Si O O
+O +O O O

Ph Ph Ph Ph
-
Me3Si O
+O

Ph

8. (15 pts) Suggest a plausible arrow-pushing mechanism for the following reaction. The
reaction conditions are slightly acidic.4
O Br2 O
PyH+ Br- Br
85% PyH+ Br- = NH+
OBn CH2Cl2 OBn Br-
3 °C, 14 h

Answer:
A H
O O :O
+ Br
:Br Br Br Br

-Br :
OMOM OMOM OMOM

: A- -A: H
H O+ HO: O + O
H
Br Br Br Br
Br Br

OMOM OMOM OMOM OMOM

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Chem 201 Name:_________________________

9. (20 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.56 Don’t
worry about the stereochemistry.
O

Me3SiO Me3SiO Me3SiOTf Ph

+
Ph Ph O Ph CH2Cl2 Ph O Ph
-78 °C

Answer:
OTf OTf
SiMe3 Me3Si -
.. + SiMe3
Me3SiO Me3SiO + Me3SiO

Ph O Ph Ph O Ph Ph O
.. Ph

Nu Me
Me3Si Si 3
Me3SiO: O+ - O+ O
Nu:
Ph Ph Ph Ph

Ph O Ph Ph O Ph Ph O Ph Ph O Ph
+

10. (15 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.7 Don’t
worry about the stereochemistry.

O O
B B
O O O O O O 89%
pentanes
Ph 25 °C, 14 h Ph

Answer:

O - O O - O O
O B B
+ +O B
B :O O O O O O
O O :O
Ph Ph Ph
Ph

I would accept O - O
a pericyclic B +
[3,3]-sigmatropic O O
rearrangement
Ph

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Chem 201 Name:_________________________

11. (15 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.8
N
N NaCNBH3
AcOH 68%
20 °C, 1 h
N N
H

Answer:
. +N
N N. N

N N H -
N
.. + B CN N
H H
H A H H H

12. (15 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.9
SiMe3
ZnCl2 O
CHO CHCl3 93%
reflux
SiMe3
Answer:
-
ZnCl2
+
O
SiMe3

- =
O: ZnCl2 O ZnCl2
+
SiMe3 SiMe3

X
..
X Me3Si X
- - - X
Cl2Zn Cl2Zn - Cl2Zn -
SiMe3 SiMe3 - + Si Me3 - SiMe3 SiMe3
O O O: Cl2Zn O Cl2Zn +
O O
+ +

-
Cl2Zn SiMe3
I am much less enthusiastic about this
O: + intramolecular silyl transfer
H due to the geometry and O-Si distance

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Chem 201 Name:_________________________

13. (10 pts) Circle the major diastereomer expected in the following reaction and say whether
you expect it to form under Felkin-Anh control or chelation control.
OBn OBn OH

MeOCH2O OBn OCH2OMe

OBn OBn O
ZnBr2 chelation
Bu3Sn 90
..
CH2Cl2 10 OBn OBn OH
MeOCH2O OBn OCH2OMe

MeOCH2O OBn OCH2OMe

ZnBr2 must coordinate to the C=O for activation. Felkin-Anh

Zn+2 salts are good for chelation.
5-membered ring chelate is better than 6-membered ring

O O
- Br2 - Br2
R MeOH2CO Zn O+ Zn O
= MeO approaches MeO
H
OCH2OMe R O from the top O
bottom face
is hindered R R
b/c of R SnBu3

14. (20 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.10
O O
Li
O O O O 89%
THF
OMe - 20 °C, 10 h
TBSO TBSO

Answer:
- - O
Li + Li Li Li
AcO O: O AcO O O: AcO O O+ O :O O

R OMe R OMe R OMe R OMe

..
-O -O O
Li
O O+ O O O O - O: O O

R OMe R OMe R OMe

-
:O OMe O :O - O
H :B
O O O O

R OAc R OAc R OAc R

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Chem 201 Name:_________________________

15. (20 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.11
OBn
O O >95%
N2 2,4,6-collidine
2,4,6-collidine
BnOH is a high-boiling
O O pyridine derivative
180 °C N

Answer:

- O H
- O :O :OBn
N + C
..N +
N N

O O O

B:
H
OBn .. OBn B OBn
-O + -O H O
H

O O O

16. (15 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.12

O NaH O
O C6H5CH2Br O
85%
HO THF OCH2C6H5
O 23 °C O

Answer:

O O O O
Na O O O O
H
H Ph
O -O
.. O
.. - Br OCH2C6H5
O O O O

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Chem 201 Name:_________________________

17. (15 pts) Suggest a plausible arrow-pushing mechanism for the following reaction.13

HO
N N
Ph HCl Ph
Ph Ph 46%
AcOH
reflux, 2 h

Answer:
HO +H
.. N 2O
A H N N N
Ph Ph Ph Ph
Ph Ph + Ph Ph
H : A-

stable carbocation

References

1
Cerero, S.; Martinez, A.G.; Vilar, E.T.; Fraile, A.G.; Maroto, B.L. J. Org. Chem. 2003, 68,
1451–1458.
2
Mandelt, K.; Meyer-Wilmes, I.; Fitjer, L. Tetrahedron 2004, 60, 11587–11596.
3
a) Hassner, A.; Reuss, R. H.; Pinnick, H.W. J. Org. Chem. 1975, 40, 3427–3429. b)
Rubottom, G. M. Vazques, M.A.; Pelegrina, D.R. Tetrahedron Lett. 1974, 4319-4322. c) acid-
catalyzed ring opening: Brook, A. G.; Macrae, D.M. J. Organometal. Chem. 1974, 77, C19-
C21.
4
This is an intentional oversimplification of the reagent, pyridinium hydrobromide perbromide,
PyH+ Br3-: Dauben, W. G.; Warshawsky, A. M. J. Org. Chem. 1990, 55, 3075–3087
5
Kanwar, S.; Trehan, S. Tetrahedron Lett. 2005, 46, 1329-1332
6
Lin, C.-H.; Matyjaszewski, K. J. Pol. Sci. A: Pol. Chem. 1990, 28, 1771–1779.
7
Hoffmann, R. W.; Ditrich, K.; Froech, S. Liebigs Ann. Chem. 1987, 977–986. Actually, the
authors used petroleum ether – an inexpensive mixture of volatile hydrocarbons.
8
Kozmin, S. A.; Iwama, T.; Huang, Y.; Rawal, V. H. J. Am. Chem. Soc. 2002, 124, 4628–
4641.
9
Takahashi, K.; Akao, R.; Honda, T. J. Org. Chem., 2009, 74, 3424–3429.
(amylene was included as a solvent stabilizer)
10
Keck, G. E.; Li, X.-Y.; Knutson, C.E. Org. Lett., 1999, 1, 411–414.
11
Rao, Y.K.; Nagarajan, M. J. Org. Chem. 1989, 54, 5678–5683.
12
Hesek, D.; Lee, M.; Zhang, W.; Noll, B.C.; Mobashery, S. J. Am. Chem. Soc. 2009, 131,
5187–5193.
13
Lyle, R.E.; Fielding, H. L.; Cauquil, G.; Rouzaud, J. J. Org. Chem. 1955, 20, 623–626.