Practice Problems, November 27, 2000

1. Why do the following groups all have very similar A-values?

R-Group
A-Value (kcal mol-1)
1.74
CH3
1.79
CH2CH3
1.77
CH2CN
1.79
CH2Br
1.79
CH2Sn(CH3)3
1.65
CH2Si(CH3)3
1.68
CH2Ph
2. What is the product of the following mercuration reaction?
Hg(NO 3 )2

NaBH 4

CH 3 CN

C 8 H 15 NO

Give a mechanism for its formation.

3. Predict the products of the following epoxidations. Only one equivalent of mCPBA is
present in each case.
mCPBA
CH2Cl2
O

mCPBA
OCH3

H
C
H

CH2Cl2

CH3 mCPBA
CH3

CH2Cl2

4. Provide a mechanism to explain the following unexpected transformation.

I2, KI

OH

NaHCO3 (aq.)
COOH

5. Hydroboration of an alkene is usually followed by oxidation. If the oxidation is done using

H2O2/NaOH, the product is an alcohol. What is the product of the following reaction?
1) B2H6, THF
2) H2NOSO3H

Answers to Practice Problems, November 27, 2000

1. Why do the following groups all have very similar A-values?
R-Group
A-Value (kcal mol-1)
1.74
CH3
1.79
CH2CH3
1.77
CH2CN
1.79
CH2Br
1.79
CH2Sn(CH3)3
1.65
CH2Si(CH3)3
1.68
CH2Ph
The A-value (conformational free energy) of an R-group on a cyclohexane ring arises
primarily from the steric repulsion between an axial R-group and the H-atoms that are
synaxial on positions 3 and 5. When the R-group is not symmetrical, it too has
conformational freedom. Rotation around the CC bond linking R to the ring encounters a
3-fold barrier, and the lowest energy minimum for CH2X will be the rotamer having the
group X outboard with respect to the ring. Note that this means that the synaxial steric
interaction is largely due to the CH2 fragment. The bulk of the X fragment will only
contribute when the R-group is in one of the higher-energy geometries. For this reason,
most groups CH2X have nearly the same A-value as CH3.
H X

HH X
H
H

H
H

2. What is the product of the following mercuration reaction?

Hg(NO 3 )2

NaBH 4

CH 3 CN

C 8 H 15 NO

Give a mechanism for its formation.

NO3
Hg(NO3)2

Hg(NO3)

Hg(NO3)
N

N CCH3
Hg(NO3)
N

CH3

Hg(NO3)
N

OH
H

CH3

C
O

Hg(NO3)

N C CH3
O H

Hg(NO3)
N

Hg(NO3)

H2O added
with the NaBH4
workup step

CH3

CH3

CH3

This hydration/tautomerization will

probably occur very rapidly. It could
proceed by an acid-catalyzed route as
shown here, although since solutions
of NaBH4 in water are basic, a basecatalyzed mechanism is perhaps more
likely.

NaBH4

HgH
N
H

C
O

CH3

The remainder of the mechanism

is identical to the general pathway
for free-radical reduction of
organomercury species that is
described in the textbook.

3. Predict the products of the following epoxidations. Only one equivalent of mCPBA is
present in each case.
O

mCPBA
CH2Cl2
O

mCPBA
OCH3

H
C
H

CH2Cl2

CH3 mCPBA
CH3

CH2Cl2

OCH3
O
H

CH3
CH3

All of these epoxidations involve reaction of the more electron rich alkene group. Note that
steric effects of the alkene substituents have a minimal effect on reactivity because approach
of the peroxyacid is nearly perpendicular to the plane of the alkene. The substituents are all
oriented more or less in the plane, except in the last case. Notice that in this allene structure,
the CH3 groups will overhang the other alkene because the molecule is not planar.

4. Provide a mechanism to explain the following unexpected transformation.

OH

I2, KI
NaHCO3 (aq.)
COOH

I
NaHCO3 (aq.)

I2, KI
O

COO

COOH

C
O

OH
HCO3

I
H 2O

The intended reaction was an iodolactonization. However, this particular system is not set
up appropriately. Recall that halolactonizations will tend to favor the Markovnikov product.
In this system, the Markovnikov pathway would require forming a 4-membered lactone ring.
While this is possible, it is a strained situation. The alternative 5-membered ring lactone
must form via an intermediate that puts more cationic character on the less-substituted C
atom. Because these pathways are less favorable, and because the iodonium ion positions a
good leaving group with respect to the carboxylate, it is possible to eliminate CO2.

5. Hydroboration of an alkene is usually followed by oxidation. If the oxidation is done using

H2O2/NaOH, the product is an alcohol. What is the product of the following reaction?
H
NH2

1) B2H6, THF
2) H2NOSO3H
R
R3B

+ H2NOSO3H

B NH OSOH
R

R2B NHR
+
HSO4

Notice the similarity between this reagent and the HOO anion in the conventional oxidative
workup. In both cases, we have a nucleophile with a built-in leaving group (i.e. :NuX).
Thus, when the nucleophile attacks the tri-coordinate boron to form the anionic intermediate,
migration of an R-group with expulsion of the hydrogensulfate ion (an excellent leaving
group, the conjugate base of a very strong acid) is straightforward. The oxidative workup
probably also requires the addition of a base, which was not indicated in the problem.