CHEM 281 Module 10 Practice Problems

These practice problems should be completed while the chapter material is covered in lecture. They are not turned in for credit. An answer key will be
posted.

N
Br OH
2-ethyl-4,4-dimethylpent-1-ene (R,S)-4-bromo-2,2,4-trimethylhexane (R,S)-3,5,5-trimethylhexan-3-ol
P
must have bromine atom here only
one elimination product

must have this stereochemistry

to form Z-alkene L
Br M
(3R,4R)-3-bromo-2,2,4-trimethylhexane (Z)-2,2,4-trimethylhex-3-ene
and (3S,4S)-3-bromo-2,2,4-trimethylhexane

Remember that an antiperiplanar arrangement of the H–C–C–Br fragment is required for E2 elimination.

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1. Jonathon Chemist took 2,3-dimethylbutane-2,3-diol and treated it with acid (H3O+) in order to try and form an alkene. However,
the product that he obtained was 3,3-dimethylbutan-2-one. Draw a mechanism for this reaction and comment on the stability of
any cationic intermediates. First, draw the reactant and product: different carbon framework => rearrangement.
O
+
H3O
HO OH

2,3-dimethylbutane-2,3-diol 3,3-dimethylbutan-2-one

HO OH HO O H HO +H2O
H
H H
O
H
H H2O H
O

More stable cation is that adjacent to the oxygen atom and this is the driving force for the rearrangement.
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2. Draw the major product formed and name it according to IUPAC convention (you do not have to
name the product formed in part d) clearly identifying any stereochemistry in the product:-

a Br
1) BH3:THF -
2) H2O2/HO
then PBr3
(+ enantiomer)
(1R*,2S*)-1-bromo-2-methylcyclohexane

b 1) Hg(OAc)2:MeOH
-
2) NaBH4/HO OMe
1-methoxy-1-methylcycloheptane

c OH
MeO
CH3OH/H+

(1S,2S)-2-methoxy-2-methylcyclohexan-1-ol

1) BH3:THF -
d 2) H2O2/HO
O
then Na(s) followed by
CH3I
3. Suggest a route, i.e. reagents and conditions, to prepare the following substances beginning
with the stated starting material and any other reagent you wish to use.
a) (E)-hex-2-ene from hex-1-ene
NaOEt
HBr Br EtOH

b) 3-bromo-3-methylcyclohexene from 3-methylcyclohex-2-en-1-ol

HBr
PBr3 Br

pyridine
Br Does not OH
involve allylic cations
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 c) tetrahydrofuran from 4-bromobutan-1-ol
K+ O
Br
OH

d) (2R*,3S*)-3-methylpentane-2,3-diol from (2R,3R)-2-bromo-3-methylpentane (3 steps)

Br
NaOEt/ EtOH RC(O)O2H O

OH + enantiomer
either H2O/H+
+ enantiomer
or NaOH/H2O OH

4. Oxiranes can be transformed into thiiranes using the reagent Ph3P=S. Given below is the
mechanism for this reaction on oxirane itself. Draw the product of this reaction sequence when
the oxirane used is (R)-2-methyloxirane.
O
O
O S O S
S P
S P
P Ph Ph Ph Ph
Ph Ph P Ph Ph
Ph Ph Ph
Ph
nucleophilic attack on
least crowded carbon

S
O
S + P O S
Ph Ph O
Ph P P
Ph Ph Ph Ph Ph
Ph
(S)-2-methylthiirane
NOTE: reaction occurs with an inversion of
configuration on both carbons of the oxirane

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5. (S)-4-(1,1-dimethylethyl)cyclohexene can be dihydroxylated by formation of an oxirane using
peracetic acid followed by basic ring opening with NaOH.
a) There are 4 possible stereoisomers, i.e. 2  2 for the two new stereocentres.
b) There are no meso structures
c) Draw the products of the ring opening reaction in their most stable conformations (hint:
the dimethylethyl group is always equatorial).

nucleophilic
attack at C-1

1
OH
2 O OH
nucleophilic attack
at C-2

two oxirane diastereomers are OH

produced with peracetic acid 1 OH
2 O
nucleophilic attack
at C-2
each oxirane
diastereomer
can be opened at either
end to produce two OH
diastereomeric diols OH OH

OH

note only two

diastereomers OH
are produced
OH

d) Assign (R) and (S) descriptors to the products from part c.

Compound on left is (1S,2S,4S) and compound on right is (1R,2R,4S)
e) What is the relationship between the products from part
c. They are DIASTEREOMERS

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6. Devise effective reaction schemes in order to synthesize the following compounds. Use the given starting materials and any
other reagents needed. Clearly indicate the reagents and conditions used.

A MeOH
Cl KOtBu 1) Hg(OAc)2
- O
2) NaBH4/HO
1-chloro-3-methylbutane

B
1) BH3:THF OH PBr3 Br NaCN CN
-
2) H2O2/HO pyridine DMSO

3-methylbut-1-ene

C Br
NaOH OH
NaOEt/EtOH CH3CO 3H
H2O OH
(+ enantiomer) acid-catalyzed opening in
1- bromo-1-methylcyclohexane
water works as well

1) NaNH2 OH H OH
CH3CO3H O
D H3C H
2

2) 2,2-dimethyloxirane Lindlar's
2- methylbut-1-ene

E
1) BH3:THF KOtBu
Br -
2) H2O 2/HO
(S)-4-bromo-3-methybut-1-ene
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F KOtBu
HBr H
goes via
Br relief of ring strain

G
NaOMe
MeO (+ enantiomer)
O MeOH HO
(+ enantiomer)
(Z)-3-methylpent-2-ene (2R,3R)-2-methoxy-3-methylpentan-3-ol

1) BH3:THF TsCl NaOEt/EtOH

H -
2) H2O2/HO OH pyridine OTs
1- methylcyclohexene (+ enantiomer) (+ enantiomer) (+ enantiomer)

1) BH3:THF PBr3 CH3CO3H O

I OH Br
-
1) H2O2/HO pyridine

1) NaNH2 1) NaNH2 H2/Pd OH

H H H
2) 1-bromopropane 2) 2-methyloxirane
HO

HBr Br KOtBu
J

3,3-dimethylbut-1-ene
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8a) Draw the most stable chair conformation of (1S,2R,4S)-1,2,4-trimethylcyclohexane.

or

b) Vitamin A (C20H30O) contains one hydroxyl group and one ring. How many -bonds does vitamin A
contain?
IHD = 6 and there is one ring therefore, there are 5 -bonds in vitamin A.
c) Cholestane (C27H48) contains no aromatic rings and it consumes zero moles of hydrogen gas
during catalytic hydrogenation, how many rings does cholestane contain?
IHD = 4 with no -bonds or aromatic rings means that cholestane contains four rings.
9. A cis alcohol (A) of molecular formula C9H18O when reacted with tosyl chloride (CH3C6H4SO2Cl) in
pyridine gives an optically active compound (B). Reaction of this tosylate with sodium iodide in acetone
yields (1S,3S)-1-iodo-3-(1-methylethyl)cyclohexane (C).
i. Name the starting alcohol A and draw the most stable chair conformation for this alcohol.

OH or
HO

(1R,3S)-3-(1-methylethyl)cyclohexanol
ii. Draw the tosylate B

O
O S O
OTs or

iii. Draw the most stable chair conformation of the reaction product when C is reacted with sodium cyanide
in DMSO.

CN or
NC
10. Draw stereo structures of compounds D and E:
PBr3 NaO2CCH3
(R)-hexan-2-ol D E
DMSO
O

Br O
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