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Application of the carbonyl epoxide rearrangement to the formation of dioxabicycloalkanes and alkenes. Synthesis of the mus musculus pheromone.
Tetrahedron Letters,Vo1.27,No.40,pp Printed in Great Britain
4909-4912,1986
0040-4039/86 $3.00 + .OO Perqamon Journals Ltd.
APPLICATIONOF TRE CARBONYLRPOXIDE REARRANGEMENT TO ‘IHE FORMATIONOF DIOXABICYCLOALKANESAND ALKRNES. SYNTHESIS OF THE m Barry Department
Abstract: general mosculns
G.s-epoxy
ketone
manner
to yield
under
acid
including
Chemistry,
Yale
Wolff
and Teruo
University,
earlier
we
reported
(a)
by
a carbonyl
ring
proceeds
(i) -E-brevicomin
products by
communication1
catalysis,
configuration our
of
Steven
Oku
New Eaven.
(SI
06511
Acid-catalyzed intramolecular opening of epoxides by carbonyl groups stereocontrolled method for forming dioxabicyclo systems, including pheromone and products corresponding to certain insect pheromones.
In an earlier
place
H. Wasserman,*
MUSCULUSPKEROMONE.
and may be in the
opening
family of
as illustrated findings
Q&).2
of
the in
3 on the
employed insect epoxide
that
We now report
(1)
of
rearrangement that
to
pheromones.
the ZnC12-catalyzed
rearrangement
epoxide
generally’
by
this
opening
reaction
The transformation
process of
carbonyl
oxygen.
(Scheme epoxy
1).
carbonyl
of
a
the
in a stereoselective occurs
form bicyclodioxaalkanes
the
a series
intramolecular
the
provides the (+1-b
of
appears with Table
readily type to
inversion 1
3.
take of
summarizes
compounds.
R3=Et n-l
Me
Me
0’
R3=Et n=l 4909
3
Scheme 1
4910
Table
Conversion
1.
a) Rearrangement (CB3) 2co; 3b recovery
c)
of
conditions
the
insect
This (Z) - or is
the
Novotny4
(f)
racemic
form
of
the
also
(pale B
yellow
conditions
of PhS03H
in CC14; 3b d) rearranged
SnCl,,
under
in
(20%
reaction
by other
routes.
provided alkylation oil)
(house
(la)
mouse)
with &
is
(la),
formed
pheromone
shown
in
Scheme
(Z)-1-bromo-Z-pentene (67%)
product (85%)’
product
unsaturated as
analogs.
outlined
below.
isolated
recently
by
5.6,7
(+)-pheromone (4)
The exe
the
to
as
(a)
which
a
was
was
Alkylation
(prepared
from
colorless
smoothly
then
2.
oil
oxidized
treated
with
of
the
commercially
after
column
by PCC to yield MCPBA to
give
the the
(86%) .l”
Hydrogenation product
Trace
100°.1’3a
extended
(8a,b). musculus
P-pentenyl-l-01)
(&)
be
&
the
The
at
ketone
b)
frontalin
of DL-Z-hydroxy-3-butyne
8
neat
support);3b
CP3CDOB catalysis epoxy
3t
to Diorabicycloa1kaner
product
may
and synthesized
(Z) -epoxide
mild
of
on a basic
using
Heated
(E)-6,7-epoxy-3-nonen-Z-one
chromatography.
a major
f)
Derivatives
Intermediate
a trioxabicyclo
rearrangement
available
ketone
e)
0°);3b
pheromone,
Our synthesis dianion
reaction
ketone);3b
(MCPBA at
Carbonyl
100 e (SE-30
VPC at
Instantaneous
epoxy
t including +
during
of Epoxy
of B (55%)11 of
(Lindlar along
reduction
with
catalyst, 11% of
quinoline) the
in CB2C12 sufficed
desired
afforded natural
to permit
the &-intermediate product
(la).
some intramolecular
(&)
as
Apparently,
the
cyclization
to
4911
5a
6a
7a
8a
5b
8b
lb
Scheme
the
bioyclic
system.
with
various
Levis
rearrangement (+)-exo-u
To accomplish Acids
proceded mascalns
In
parallel
(BF8*Et20, cl eenly
pheromone work,
we
hydrogenation
(Lindler
catalyst).
isomer
under
could
be isolated
(lb) systems
intrsmoleculer stereospecifioelly, The resulting to
those
es
related
ring with
silicic
smoothly
only
to
&
the
sole
opening inversion
1.
of
in
the
Z-step
(ml
frontalin. e-poxide
oyclisetion
through through
to
stable
followed
then
ZnC12 es
in
(&l
changes
the
formation Table
takes
transition
by cis
ketone
in the
oxygen
oonformetionel
the
afforded
shorn
e chair-like
the
with
3!?
epoxy
products cerbonyl
end gave
sequence
that.
The
yield.5
unsetureted
We suggest
the
ZnClg
converted
more
(8a)
examined.
quantitative
of &with
end other by
of
epoxide
of
wes
oxidation
was
Treatment
reaction
case
be
end this
(100%) .13
of configuration undergoes
ZnClI)
above
0il1.l~
the
acid,
could
product
product
the
3
of hydrogenation.
(colorless
then
by the
to la.
in nearly
compound
The trens
to brevicomin,
intermediate
shown in Scheme
BTsOB,
that
conditions
in 88% yield
(f)-a-derivative of bioyclio
then
conversion
stereospecifically
found
end
the
end (la)
(E)-1-bromo-Z-pentene
(&A)
complete
2
1,
place state. similar
4912
Acknowledgment: with
Comparison
spectroscopic
of synthetic
data kindly provided
pheromone
(la) with
the natural
material
was
made
by Dr. S. Danishefsky.
References
8.8.;
2.
For other syntheses of brevioomin, see: a) Bellas. T.E.; Brownlee. R.G.; Silverstein. R.M. Tetrahedron 1969, 25, 5149; Schafer, E.J.; Angew. Chem. Int. Ed. Enal. b) Knolle. J.; 1975, 14, 758; c) Sum. P.-E.; Weiler, L. Can. J. Chem. 1979, 51. 1475; d) Kufner, U.; Schmidt, R.R.; Svnthesis 1985, 1090.
3.
Ph.D. dissertation, Yale University, 1969; a) Barber, E.E. b) Wolff, S. Ph.D. dissertation, Yale University, 1971.
4.
Wieser,
5.
A synthesis of h mnscalus pheromone reported by Danishefsky, illnstrates of aldehydes and dienes: diastereofacial control in the Lewis Acid cyclocondensation Danishefsky. S.J.; Pearson, W.H.; Harvey, D.F. J. Am. Chem. Sot. 1984, 106. 2455.
6.
For a non-stereospecific synthesis J. Ora. Chem. 1984, $9. 5264.
7.
Bhupathy, M.; Cohen, T. stereoselective syntheses
8.
'Ii NMR (90 MHz, CDCl )s 0.99 (3 R t J = 7.5 As) 1.44 (3 B, d J = 6 Rz) 2.08 (2 R. m). 2.50 (1 H, d. J 2 5 HZ). 2.97'(2'8, d. J = 5 is), 4.50 (1 A: m). 5.20-4.64 (2 8. m). IR (CHC13) 3420, 2975, 2945, 2880. 1445. 1410, 1365. 1250 cm-l.
9.
ill NMR (90 kills.CDCl )8 1.00 (3 K t J = 7.5 Hz). 1.91-2.27 (2 A. m). 2.31 (3 8. s). 3.12 (2 8, d. J = 6 is), 5.17-5.76 (; B, m). IR (CRC13) 3040, 3000, 2960, 2910. 1695, 1620, 1430, 1385 cm-l.
Schwende.
E.H.;
1969. 91. 3674.
Wasserman,
D.P.;
Barber,
J. Am. Chem. Sot.
1.
F.J.;
Carmack,
M.;
Novotny,
of the pheromone
Tetrahedron Letters of & and la.
1985,
M.
la,
26.
J. Ora. Chem.
see Mnndy.
2619
B.P.;
have
1984, 49. 882.
Bornmann.
recently
reported
10.
'R NMR (CDC13)8 1.11 (3 H. t, J = 7.5 Ez), 1.33-1.80 (2 A, m). 2.37 (4H. m). IR (CEC13) 3080, 3000, 2970, 2910, 1695. 1620. 1430, 1185 cm-l.
11.
Ill NMR (90 REC. CDCl ) 8 1.06 (3 H t J= 7.5 Hz), 1.35-1.75 (2 H. m) 2.24 (3 8. s). 2.70-3.23 (4 A. m), 3.10-6.45 (2 8: mi. IR (CEC13) 3040, 3000, 2965. 2910, 1695, 1620, 1430, 1180 cm-l.
12.
%l NMR (90 MHz, CDCl )s 0.99 (3 8, t. J= 7.5 Hz), 1.42-1.75 (2 8. m). 2.22 2.66-3.20 (4 8. m). 3.92-6.35 (2 H, m). IR (CHC13) 3045, 3010, 2975, 2920, 1695, 1625, 1425. 1185 cm-l.
13.
1H NMR (250 kfllr,CDCl )8 0.99 (3 R t J= 7.5 Hz) 137-1.81 2.07 (1 H, m). 2.63 (1 8, m), 4.08'(1'A, q. J = L'Asj, 4.62 A, m). 5.90 (1 A, dt, J = 10 Hz, 2 Ez). (Received
in
UK
4 August
1986)
W.G.
(3 H. s), 2.51-3.30
(3 8. s).
(2 H. m). 1.52 (3 8. s). (1 H, t, J = 6 Hz). 5.67 (1
4909-4912,1986
0040-4039/86 $3.00 + .OO Perqamon Journals Ltd.
APPLICATIONOF TRE CARBONYLRPOXIDE REARRANGEMENT TO ‘IHE FORMATIONOF DIOXABICYCLOALKANESAND ALKRNES. SYNTHESIS OF THE m Barry Department
Abstract: general mosculns
G.s-epoxy
ketone
manner
to yield
under
acid
including
Chemistry,
Yale
Wolff
and Teruo
University,
earlier
we
reported
(a)
by
a carbonyl
ring
proceeds
(i) -E-brevicomin
products by
communication1
catalysis,
configuration our
of
Steven
Oku
New Eaven.
(SI
06511
Acid-catalyzed intramolecular opening of epoxides by carbonyl groups stereocontrolled method for forming dioxabicyclo systems, including pheromone and products corresponding to certain insect pheromones.
In an earlier
place
H. Wasserman,*
MUSCULUSPKEROMONE.
and may be in the
opening
family of
as illustrated findings
Q&).2
of
the in
3 on the
employed insect epoxide
that
We now report
(1)
of
rearrangement that
to
pheromones.
the ZnC12-catalyzed
rearrangement
epoxide
generally’
by
this
opening
reaction
The transformation
process of
carbonyl
oxygen.
(Scheme epoxy
1).
carbonyl
of
a
the
in a stereoselective occurs
form bicyclodioxaalkanes
the
a series
intramolecular
the
provides the (+1-b
of
appears with Table
readily type to
inversion 1
3.
take of
summarizes
compounds.
R3=Et n-l
Me
Me
0’
R3=Et n=l 4909
3
Scheme 1
4910
Table
Conversion
1.
a) Rearrangement (CB3) 2co; 3b recovery
c)
of
conditions
the
insect
This (Z) - or is
the
Novotny4
(f)
racemic
form
of
the
also
(pale B
yellow
conditions
of PhS03H
in CC14; 3b d) rearranged
SnCl,,
under
in
(20%
reaction
by other
routes.
provided alkylation oil)
(house
(la)
mouse)
with &
is
(la),
formed
pheromone
shown
in
Scheme
(Z)-1-bromo-Z-pentene (67%)
product (85%)’
product
unsaturated as
analogs.
outlined
below.
isolated
recently
by
5.6,7
(+)-pheromone (4)
The exe
the
to
as
(a)
which
a
was
was
Alkylation
(prepared
from
colorless
smoothly
then
2.
oil
oxidized
treated
with
of
the
commercially
after
column
by PCC to yield MCPBA to
give
the the
(86%) .l”
Hydrogenation product
Trace
100°.1’3a
extended
(8a,b). musculus
P-pentenyl-l-01)
(&)
be
&
the
The
at
ketone
b)
frontalin
of DL-Z-hydroxy-3-butyne
8
neat
support);3b
CP3CDOB catalysis epoxy
3t
to Diorabicycloa1kaner
product
may
and synthesized
(Z) -epoxide
mild
of
on a basic
using
Heated
(E)-6,7-epoxy-3-nonen-Z-one
chromatography.
a major
f)
Derivatives
Intermediate
a trioxabicyclo
rearrangement
available
ketone
e)
0°);3b
pheromone,
Our synthesis dianion
reaction
ketone);3b
(MCPBA at
Carbonyl
100 e (SE-30
VPC at
Instantaneous
epoxy
t including +
during
of Epoxy
of B (55%)11 of
(Lindlar along
reduction
with
catalyst, 11% of
quinoline) the
in CB2C12 sufficed
desired
afforded natural
to permit
the &-intermediate product
(la).
some intramolecular
(&)
as
Apparently,
the
cyclization
to
4911
5a
6a
7a
8a
5b
8b
lb
Scheme
the
bioyclic
system.
with
various
Levis
rearrangement (+)-exo-u
To accomplish Acids
proceded mascalns
In
parallel
(BF8*Et20, cl eenly
pheromone work,
we
hydrogenation
(Lindler
catalyst).
isomer
under
could
be isolated
(lb) systems
intrsmoleculer stereospecifioelly, The resulting to
those
es
related
ring with
silicic
smoothly
only
to
&
the
sole
opening inversion
1.
of
in
the
Z-step
(ml
frontalin. e-poxide
oyclisetion
through through
to
stable
followed
then
ZnC12 es
in
(&l
changes
the
formation Table
takes
transition
by cis
ketone
in the
oxygen
oonformetionel
the
afforded
shorn
e chair-like
the
with
3!?
epoxy
products cerbonyl
end gave
sequence
that.
The
yield.5
unsetureted
We suggest
the
ZnClg
converted
more
(8a)
examined.
quantitative
of &with
end other by
of
epoxide
of
wes
oxidation
was
Treatment
reaction
case
be
end this
(100%) .13
of configuration undergoes
ZnClI)
above
0il1.l~
the
acid,
could
product
product
the
3
of hydrogenation.
(colorless
then
by the
to la.
in nearly
compound
The trens
to brevicomin,
intermediate
shown in Scheme
BTsOB,
that
conditions
in 88% yield
(f)-a-derivative of bioyclio
then
conversion
stereospecifically
found
end
the
end (la)
(E)-1-bromo-Z-pentene
(&A)
complete
2
1,
place state. similar
4912
Acknowledgment: with
Comparison
spectroscopic
of synthetic
data kindly provided
pheromone
(la) with
the natural
material
was
made
by Dr. S. Danishefsky.
References
8.8.;
2.
For other syntheses of brevioomin, see: a) Bellas. T.E.; Brownlee. R.G.; Silverstein. R.M. Tetrahedron 1969, 25, 5149; Schafer, E.J.; Angew. Chem. Int. Ed. Enal. b) Knolle. J.; 1975, 14, 758; c) Sum. P.-E.; Weiler, L. Can. J. Chem. 1979, 51. 1475; d) Kufner, U.; Schmidt, R.R.; Svnthesis 1985, 1090.
3.
Ph.D. dissertation, Yale University, 1969; a) Barber, E.E. b) Wolff, S. Ph.D. dissertation, Yale University, 1971.
4.
Wieser,
5.
A synthesis of h mnscalus pheromone reported by Danishefsky, illnstrates of aldehydes and dienes: diastereofacial control in the Lewis Acid cyclocondensation Danishefsky. S.J.; Pearson, W.H.; Harvey, D.F. J. Am. Chem. Sot. 1984, 106. 2455.
6.
For a non-stereospecific synthesis J. Ora. Chem. 1984, $9. 5264.
7.
Bhupathy, M.; Cohen, T. stereoselective syntheses
8.
'Ii NMR (90 MHz, CDCl )s 0.99 (3 R t J = 7.5 As) 1.44 (3 B, d J = 6 Rz) 2.08 (2 R. m). 2.50 (1 H, d. J 2 5 HZ). 2.97'(2'8, d. J = 5 is), 4.50 (1 A: m). 5.20-4.64 (2 8. m). IR (CHC13) 3420, 2975, 2945, 2880. 1445. 1410, 1365. 1250 cm-l.
9.
ill NMR (90 kills.CDCl )8 1.00 (3 K t J = 7.5 Hz). 1.91-2.27 (2 A. m). 2.31 (3 8. s). 3.12 (2 8, d. J = 6 is), 5.17-5.76 (; B, m). IR (CRC13) 3040, 3000, 2960, 2910. 1695, 1620, 1430, 1385 cm-l.
Schwende.
E.H.;
1969. 91. 3674.
Wasserman,
D.P.;
Barber,
J. Am. Chem. Sot.
1.
F.J.;
Carmack,
M.;
Novotny,
of the pheromone
Tetrahedron Letters of & and la.
1985,
M.
la,
26.
J. Ora. Chem.
see Mnndy.
2619
B.P.;
have
1984, 49. 882.
Bornmann.
recently
reported
10.
'R NMR (CDC13)8 1.11 (3 H. t, J = 7.5 Ez), 1.33-1.80 (2 A, m). 2.37 (4H. m). IR (CEC13) 3080, 3000, 2970, 2910, 1695. 1620. 1430, 1185 cm-l.
11.
Ill NMR (90 REC. CDCl ) 8 1.06 (3 H t J= 7.5 Hz), 1.35-1.75 (2 H. m) 2.24 (3 8. s). 2.70-3.23 (4 A. m), 3.10-6.45 (2 8: mi. IR (CEC13) 3040, 3000, 2965. 2910, 1695, 1620, 1430, 1180 cm-l.
12.
%l NMR (90 MHz, CDCl )s 0.99 (3 8, t. J= 7.5 Hz), 1.42-1.75 (2 8. m). 2.22 2.66-3.20 (4 8. m). 3.92-6.35 (2 H, m). IR (CHC13) 3045, 3010, 2975, 2920, 1695, 1625, 1425. 1185 cm-l.
13.
1H NMR (250 kfllr,CDCl )8 0.99 (3 R t J= 7.5 Hz) 137-1.81 2.07 (1 H, m). 2.63 (1 8, m), 4.08'(1'A, q. J = L'Asj, 4.62 A, m). 5.90 (1 A, dt, J = 10 Hz, 2 Ez). (Received
in
UK
4 August
1986)
W.G.
(3 H. s), 2.51-3.30
(3 8. s).
(2 H. m). 1.52 (3 8. s). (1 H, t, J = 6 Hz). 5.67 (1