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302
Practice
Problems
---
Pericyclic
Reactions
1.
Which
Diels-Alder
reaction
would
you
expect
to
proceed
at
the
highest
rate?
What
would
you
expect
the
regiochemistry
and
stereochemistry
of
the
product
to
be?
a)
O H O H O H O H
b)
OMe O Me
OMe O Me
c)
OMe O H
OMe O H
2.
In
the
first
total
synthesis
of
a
steroid,
Woodward
started
with
a
Diels-Alder
reaction.
Explain
why
the
following
Diels-Alder
reaction
would
form
the
first
product
and
not
the
second.
O Me MeO O MeO O O Me not O OMe
3.
Provide
the
mechanism
of
the
following
reaction.
Would
you
perform
the
transformation
under
thermal
or
photochemical
conditions?
Justify
your
answer.
O
Me
CHEM 302 4. The photolysis of a mixture of cis and trans cyclododecaen-7-yne gave two products. Suggest which isomer gave predominantly which product and explain your choice.
H H +
hv
H H 5. The following alcohol remains stable until oxidation to the corresponding ketone. Cyclization is observed immediately. Explain this change in reactivity, provide the cyclization mechanism and reason for the stereochemistry.
6.
Although
it
gets
used
in
synthesis
all
the
time,
cyclopentadiene
is
a
somewhat
unstable
species.
Upon
standing
at
room
temperature
for
extended
periods
of
time,
it
slowly
undergoes
a
dimerization.
In
fact,
when
purchased
from
a
chemical
company
like
Aldrich,
it
is
sold
as
the
dimer
which
is
"cracked"
by
heating
at
high
temperature
(>150
C)
to
provide
the
monomeric
species
we
use
everyday.
Consider
possible
cycloaddition
pathways
([2+2],
[4+2]
and
[4+4])
and
decide
what
the
most
likely
product
would
be.
7.
Under
what
conditions,
thermal
or
photochemical,
would
you
expect
the
following
reaction
to
occur?
Me Me Me Me
2 ?
CHEM 302 8. State whether the following reaction is conrotatory or disrotatory. Under what conditions (thermal or photochemical) would you carry it out?
10.
Dewar
benzene
(shown
below
left)
is
an
interesting
molecule.
It
is
stable
at
room
temperature,
even
though
its
isomerization
to
benzene
by
an
electrocyclic
opening
of
either
cyclobutene
ring
should
be
exothermic
by
79
kcal/mol
(approximately
the
strength
of
a
carbon-carbon
bond).
Using
your
knowledge
of
the
Woodward
Hoffman
rules,
explain
why
Dewar
benzene
does
not
easily
isomerize
to
benzene.
Assuming
you
could
excite
an
electron
on
the
-bond,
would
you
expect
it
to
be
stable
to
light?
H H
11. Which pericyclic reaction is responsible for the following transformation? Under what conditions? Explain the resulting stereochemistry.
CHEM
302
12.
Predict
the
stereochemistry
of
the
product
under
the
given
conditions.
hv
a)
H H
b)
14. Explain the selectivity observed when the nine-membered ring was subjected to either thermal or photochemical conditions.
h!
H 3C
CH3 R H 3C H
CH3 R
h!
H 3C
CHEM 302 16. Provide a mechanism for the following reactions and identify the pericyclic process(es). a)
b)
H H !
OH 17. Draw a reasonable 2-step mechanism for the following (reaction under thermal conditions). OH
c)
20.
Identify
the
pericyclic
process(es)
involved
in
the
following
transformation.
Provide
a
mechanism.
Me O H ! MeO H MeO H H Me O