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Bislactonization of unsaturated diacids using lead tetraacetate
Tetrahedron Letters Vcl. 21, pp 1319 - 1822 @Pereamon Press Ltd. 198'3. Printed in Great Britain
BISLACTONIZATION
E. J. Corey of Chemistry, Harvard
Department
The reaction
Summary. lactones
OF UNSATURATED
of lead tetraacetate
(Y or 6) can be controlled
the double
bond,
in consonance
with
DIACIDS
USING
LEAD TETBAACETATE
and Andrew W. Gross University, Cambridge,
with
unsaturated
Massachusetts
carboxylic
to produce
efficiently
an initial
plumbolactonization
acids
cis addition
02138 U.S.A.
(or salts)
to form bis-
of two carboxylic
step followed
oxygens
to
by SN2 displacement
of lead. A key step in the recently the diacid
reported'
2 to the bis-Y-lactone
acetonitrile
total
synthesis
3 in 99% yield by reaction
at 25' for 1.5 hr.
This process
1,
finds
acid is converted
in 5ca. 60% yield.
into a bis-y-lactone
and mechanistic
The bislactonization
acetate with
of the -free diacid (Procedure
certain
excess
of lead tetraacetate
either
Five diverse of a disalt diacid
according
following
It is evident
a wide variety
in chloroform3
on these
substrates (Procedure
undergoes
of experimental
solution which
A').
has been
decomposition
investigated B is slower
A, the yields
that the bislactonization
utilizes
involves
satisfactory
at 80' with
a larger
the tetra-n-butylammonium (Procedure
in acetonitrile,
B).
it is ad-
or to add 15 equiv at the start of the reaction. in the Table.
than the bislactonization by Procedure
of substrates
1819
the
6 equiv of lead tetra-
found to be more
as solvent
at 75-80'
as summarized
obtained
in acetic
the scope,
with
The first procedure
6-15 equiv of lead tetraacetate
portions
with
conditions
at 20-50' with
The second procedure
at 75-80' with
lead tetraacetate
is concerned
in
bislactonization.
is the use of acetonitrile
in several
to Procedure
letter
could be defined.
conditions
significant
(4-8) were -._
Procedure
under
This
of
that endo-A4-
24
at 100° with
mediated
usually
to add 6-8 equiv
substrates
of lead(IV)
procedures
in acetonitrile
lead tetraacetate
visable
6 equiv of lead tetraacetate
in the observation'
(41 upon heating
general
A variant
less reactive
salt of the diacid Since
A).
course
was studied
that -two satisfactory
treatment
(1) was the conversion
24 acid
result
with
precedent
bicyclo[2.2.1lheptene-1,2-dicarboxylic
stereochemistry
of picrotoxinin
Although
the reaction
of the corresponding
B are in general
2, _4, _5, and 6 must
free
higher. follow
a pathway
of
cis addition
of two oxygens
For this reason cis or trans -__ pletely
d,l--
stereospecific to C=C.
was included. under
of pyridine
equiv of pyridine). > 95% specificity
by Procedure
by the Supposition
(in the Pb(III) SN2 pathway carboxylic ment
mono
becomes acid
8 under
SN1 mechanism
cis addition
cation
intermediate)
if carboxylate
can occur
stage with
with
The investigation unsaturated favorably data which
diacids with
of steric
described
is a valuable
the silver
follow
A.
provide
herein
and both c$
to the trans
salt-iodine essential
of assistance
demonstrates method
detail.
SN2 displace-
step proceeds products
lactone
_cis
vicinal
oxyqen
scope which
compares
to
groups).
(IV) induced bislactonization
4
by the
due to an SN1 prefer-
between
described.
for
will be
for stereoselective
by the neiqhboring
of considerable recently
than the
to favor stereoselective
8 is possibly
(i.e. repulsion
step the
in each case except
propensity
to
of lead
rather
trans addition,
that the second
thatthelead
bislactonization
nucleophile
B) is expected
isomer
(analogous
In the second
and trans C=C addition
The greater
with
7 and 8 are accommodated
to bislactone.
involve
100
furnished
~$2 or SN1 displacement
as is observed
(Procedure
destablization
synthetic
B, however,
of
of increasing
3:l with
plumbolactonisetion
To the extent
of bis-salts
! relative
would
_cis addition
8 as a consequence
a minimum
leading
by
of equal parts
A by the addition
ion is the displacing
to the use of free bis-acid.
shown by the -cis diacid
to a mixture
(ratio <,l to meso
by either
either
to the meso-bislactone
8 by Procedure
induced
step clearly
of Procedure
stereorandomization
formation
Pb(IV)
undergo
7 was found to be corn-
The results obtainedwith
by oxygen
lead to overall
the conditions
ence at the second
of the trans diacid
Since the first
step would
relative
of the -d,l-bislactone
and that this is followed
favorable
exclusively
of Procedure
constraints.
can in principle
of the -cis diacid
leading
Modification
step involves
Thus the bislactonization
observed.
addition
more
function.
in the second
substrate
lactone
A.
of qeometrical
7 and 8 which
8 was converted
by -cis addition.
that the first
halo or mercuri-lactonization)
studied,
amounts
Bislactonization the d,l-product
diacids
the trans diacid
led to greater
bond because
The bislactonization
all conditions
In contrast,
and meso-bislactones
amounts
double
the study of the stereoisomeric
addition
cis addition
to the carbon-carbon
of
very
The experimental
5
acid (25 mg, 0.14 mm011 was dissolved in 4 ml dry chloroform and Procedure A: Cis-4-octenedioic The solution was stirred lead tetraacetG6 (375 mg, 0.84 mmol, 6 equiv) was added in one portion. and filtered for 72 hr at 23', quenched with 20 l.ilethylene glycol, diluted with 25 mlethylacetate, The filtrate was evaporated and the residue was chromatographed on Florisil (10% through Celite. acetone-chloroform) to afford the bis-lactone of meso-4,5-cJihydroxyoctane-1,8-dioic acid (18.8 mg, 0.110 mmol, 78%) as colorless cyrstals, mp 104-1E lit. 104-10C".
TABLE
_-
- BISLACTONIZATION
SS;BSTR?iTE
PROCEDURE
c6
A,
I
30 hr,
B, 6 hr,
;tOOH COOH
!
OF SUBSTANCES
4 - 8 -. -
PRODUCT
23' 75O
YIELD,
mp
99+%,
263'
99+%,
H
48 hr,
50'
68%,
160"
B, 48 hr,
75O
85%,
I(
72 hr,
23O
B, 30 hr,
75O
60 hr,
23"
78%,
105O
g8%,
II
A,
HOOC
5 CH ,COOH
0
A,
I
CH ,COOH
s
1 C HOOC
a
COOH COOH
--l
A,
B, 26 hr,
A’ , 50 hr, 80"
/
ck--
B, 48 hr,
om
750a
b
80"
COOH
L a This
reaction
afforded
meso-bislactone
stereospecifically.
1
b Product
was
a mixture
Product
was
d,l-lactone
(ca. 1:l) -
of meso-and
d,l-bislactones.
C
with >20:1
stereoselectivity.
--
1822
trans-4-Octenedioic acid (30 mg, 0.17 mmol) was treated with tetra-n-butylammonium Procedure B: hydroxide (0.34 mmol) in methanol. The solvent was removed and the residue was azeotroped with The cyrstalline tetra-n-butylammonium salt was dissolved in 4 ml dry toluene and dried -in vacua. acetonitrile and lead tetraacetate (1.15 g, 2.6 mmoi, 15 equiv) was added. Reaction for 48 hr at 80° under argon and workup as above afforded a greater than 2O:l mixture respectively of the acid. bislactones of -d,l- and meso-4,5-dihydroxyoctane-1,8-dioic Chromatography on Florisil (10% the bislactone of d,l-4,5-dihydroxyoctane-1,8-dioic pentane - ethyl acetate 1 afforded acid (25.1 mg, 0.147 mmol, 86.4%), mp 55', lit. 55-56'. -8 Preparation of Unsaturated Diacids: Diacid ,d was prepared by the method of Diels and Alder. Cleavage of the more reactive double bond in dicyclopentadiene, followed by oxidation of the resulting dialdehyde, afforded diacid 2.' Diacid 5 was prepared by the method of Gassman and Creary." Diacid ,7 was obtained from 1,5-cyclooctadiene via epoxidation, periodate cleavage, and oxidation. lla,b Diacid 8 was prepared by two different methods. Overall olefinic inversion of dimethyl cis-4octenedioate to trans-4-octenedioate was achiev@ax$a reaction of d,&-dimethyl 4,5_dihydroryoctanedioate with dimethylformamide dimethyl acetal. ’ Dl;$cid 8 was also directly available in good eaction of 2 equiv of dilithio acetate with 1,4-dibromo-trans-2-butene (2 hr at
References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
11. 12. 13. 14. 15.
and Notes
E. J. Corey and H. L. Pearce, J. Am. Chem. Sot., s, 5841 (1979). K. Alder and S. Schneider, Liebigs Ann. Chem., 524, 189 (1936). Several equivalents of pyridine may be added to solubilize the diacid. M. Kate, M. Kageyama, R. Tanaka, K. Kuwahara, and A. Yoshikoshi, J. Org. Chem., 40, 1932(1975). Satisfactory infrared, proton magnetic resonance and mass spectrawereobtainedforeachcompound. Lead tetraacetate used in Chis work was recyrstallized from acetic acid and freed of solvent in vacua. H. E. Holmquist, F. D. Marsh. J. C. Sauer, and V. A. Engelhardt, J.Am. Chem.Soc.,g, 3681 (1959). 0. Diels and K. Alder, Liebigs Ann. Chem., 9, 98 (1928). T. Ogino and K. Mochizuki, Chem. Lett., 443 (1979). P. G. Gassman and X. Creary, Chem. Commun., 1214 (1972). (a) J. Nagarkatti and K. Ashley, Tetrahedron Letters, 4599 (1973); (b) G. Pollini, R. Tadia, A. Barco, J. Benetti, Org. Prep. and Proc. Int., 5, 217 (1974). (a) S. Hanessian, A. Bargiotti, and M. LaRue, Tetrahedron Letters, 737 (1978); Pura,TetrahedronLetters, 5223 (1970). (b) F. W. Eastwood, K. J. Harrington, T. S. JosanandJ.~. P. L. Creger, J. Org. Chem., 37, 1907 (1972). For studies of acetoxy lactonization of unsaturated carboxylic acids see, R. M. Moriarty, H. G. Walsh and H. Gopal, Tetrahedron Letters, 4363, 4369 (1966). This research was assisted financially by the National Science Foundation.
(Received
in USA 4 February
1980)
BISLACTONIZATION
E. J. Corey of Chemistry, Harvard
Department
The reaction
Summary. lactones
OF UNSATURATED
of lead tetraacetate
(Y or 6) can be controlled
the double
bond,
in consonance
with
DIACIDS
USING
LEAD TETBAACETATE
and Andrew W. Gross University, Cambridge,
with
unsaturated
Massachusetts
carboxylic
to produce
efficiently
an initial
plumbolactonization
acids
cis addition
02138 U.S.A.
(or salts)
to form bis-
of two carboxylic
step followed
oxygens
to
by SN2 displacement
of lead. A key step in the recently the diacid
reported'
2 to the bis-Y-lactone
acetonitrile
total
synthesis
3 in 99% yield by reaction
at 25' for 1.5 hr.
This process
1,
finds
acid is converted
in 5ca. 60% yield.
into a bis-y-lactone
and mechanistic
The bislactonization
acetate with
of the -free diacid (Procedure
certain
excess
of lead tetraacetate
either
Five diverse of a disalt diacid
according
following
It is evident
a wide variety
in chloroform3
on these
substrates (Procedure
undergoes
of experimental
solution which
A').
has been
decomposition
investigated B is slower
A, the yields
that the bislactonization
utilizes
involves
satisfactory
at 80' with
a larger
the tetra-n-butylammonium (Procedure
in acetonitrile,
B).
it is ad-
or to add 15 equiv at the start of the reaction. in the Table.
than the bislactonization by Procedure
of substrates
1819
the
6 equiv of lead tetra-
found to be more
as solvent
at 75-80'
as summarized
obtained
in acetic
the scope,
with
The first procedure
6-15 equiv of lead tetraacetate
portions
with
conditions
at 20-50' with
The second procedure
at 75-80' with
lead tetraacetate
is concerned
in
bislactonization.
is the use of acetonitrile
in several
to Procedure
letter
could be defined.
conditions
significant
(4-8) were -._
Procedure
under
This
of
that endo-A4-
24
at 100° with
mediated
usually
to add 6-8 equiv
substrates
of lead(IV)
procedures
in acetonitrile
lead tetraacetate
visable
6 equiv of lead tetraacetate
in the observation'
(41 upon heating
general
A variant
less reactive
salt of the diacid Since
A).
course
was studied
that -two satisfactory
treatment
(1) was the conversion
24 acid
result
with
precedent
bicyclo[2.2.1lheptene-1,2-dicarboxylic
stereochemistry
of picrotoxinin
Although
the reaction
of the corresponding
B are in general
2, _4, _5, and 6 must
free
higher. follow
a pathway
of
cis addition
of two oxygens
For this reason cis or trans -__ pletely
d,l--
stereospecific to C=C.
was included. under
of pyridine
equiv of pyridine). > 95% specificity
by Procedure
by the Supposition
(in the Pb(III) SN2 pathway carboxylic ment
mono
becomes acid
8 under
SN1 mechanism
cis addition
cation
intermediate)
if carboxylate
can occur
stage with
with
The investigation unsaturated favorably data which
diacids with
of steric
described
is a valuable
the silver
follow
A.
provide
herein
and both c$
to the trans
salt-iodine essential
of assistance
demonstrates method
detail.
SN2 displace-
step proceeds products
lactone
_cis
vicinal
oxyqen
scope which
compares
to
groups).
(IV) induced bislactonization
4
by the
due to an SN1 prefer-
between
described.
for
will be
for stereoselective
by the neiqhboring
of considerable recently
than the
to favor stereoselective
8 is possibly
(i.e. repulsion
step the
in each case except
propensity
to
of lead
rather
trans addition,
that the second
thatthelead
bislactonization
nucleophile
B) is expected
isomer
(analogous
In the second
and trans C=C addition
The greater
with
7 and 8 are accommodated
to bislactone.
involve
100
furnished
~$2 or SN1 displacement
as is observed
(Procedure
destablization
synthetic
B, however,
of
of increasing
3:l with
plumbolactonisetion
To the extent
of bis-salts
! relative
would
_cis addition
8 as a consequence
a minimum
leading
by
of equal parts
A by the addition
ion is the displacing
to the use of free bis-acid.
shown by the -cis diacid
to a mixture
(ratio <,l to meso
by either
either
to the meso-bislactone
8 by Procedure
induced
step clearly
of Procedure
stereorandomization
formation
Pb(IV)
undergo
7 was found to be corn-
The results obtainedwith
by oxygen
lead to overall
the conditions
ence at the second
of the trans diacid
Since the first
step would
relative
of the -d,l-bislactone
and that this is followed
favorable
exclusively
of Procedure
constraints.
can in principle
of the -cis diacid
leading
Modification
step involves
Thus the bislactonization
observed.
addition
more
function.
in the second
substrate
lactone
A.
of qeometrical
7 and 8 which
8 was converted
by -cis addition.
that the first
halo or mercuri-lactonization)
studied,
amounts
Bislactonization the d,l-product
diacids
the trans diacid
led to greater
bond because
The bislactonization
all conditions
In contrast,
and meso-bislactones
amounts
double
the study of the stereoisomeric
addition
cis addition
to the carbon-carbon
of
very
The experimental
5
acid (25 mg, 0.14 mm011 was dissolved in 4 ml dry chloroform and Procedure A: Cis-4-octenedioic The solution was stirred lead tetraacetG6 (375 mg, 0.84 mmol, 6 equiv) was added in one portion. and filtered for 72 hr at 23', quenched with 20 l.ilethylene glycol, diluted with 25 mlethylacetate, The filtrate was evaporated and the residue was chromatographed on Florisil (10% through Celite. acetone-chloroform) to afford the bis-lactone of meso-4,5-cJihydroxyoctane-1,8-dioic acid (18.8 mg, 0.110 mmol, 78%) as colorless cyrstals, mp 104-1E lit. 104-10C".
TABLE
_-
- BISLACTONIZATION
SS;BSTR?iTE
PROCEDURE
c6
A,
I
30 hr,
B, 6 hr,
;tOOH COOH
!
OF SUBSTANCES
4 - 8 -. -
PRODUCT
23' 75O
YIELD,
mp
99+%,
263'
99+%,
H
48 hr,
50'
68%,
160"
B, 48 hr,
75O
85%,
I(
72 hr,
23O
B, 30 hr,
75O
60 hr,
23"
78%,
105O
g8%,
II
A,
HOOC
5 CH ,COOH
0
A,
I
CH ,COOH
s
1 C HOOC
a
COOH COOH
--l
A,
B, 26 hr,
A’ , 50 hr, 80"
/
ck--
B, 48 hr,
om
750a
b
80"
COOH
L a This
reaction
afforded
meso-bislactone
stereospecifically.
1
b Product
was
a mixture
Product
was
d,l-lactone
(ca. 1:l) -
of meso-and
d,l-bislactones.
C
with >20:1
stereoselectivity.
--
1822
trans-4-Octenedioic acid (30 mg, 0.17 mmol) was treated with tetra-n-butylammonium Procedure B: hydroxide (0.34 mmol) in methanol. The solvent was removed and the residue was azeotroped with The cyrstalline tetra-n-butylammonium salt was dissolved in 4 ml dry toluene and dried -in vacua. acetonitrile and lead tetraacetate (1.15 g, 2.6 mmoi, 15 equiv) was added. Reaction for 48 hr at 80° under argon and workup as above afforded a greater than 2O:l mixture respectively of the acid. bislactones of -d,l- and meso-4,5-dihydroxyoctane-1,8-dioic Chromatography on Florisil (10% the bislactone of d,l-4,5-dihydroxyoctane-1,8-dioic pentane - ethyl acetate 1 afforded acid (25.1 mg, 0.147 mmol, 86.4%), mp 55', lit. 55-56'. -8 Preparation of Unsaturated Diacids: Diacid ,d was prepared by the method of Diels and Alder. Cleavage of the more reactive double bond in dicyclopentadiene, followed by oxidation of the resulting dialdehyde, afforded diacid 2.' Diacid 5 was prepared by the method of Gassman and Creary." Diacid ,7 was obtained from 1,5-cyclooctadiene via epoxidation, periodate cleavage, and oxidation. lla,b Diacid 8 was prepared by two different methods. Overall olefinic inversion of dimethyl cis-4octenedioate to trans-4-octenedioate was achiev@ax$a reaction of d,&-dimethyl 4,5_dihydroryoctanedioate with dimethylformamide dimethyl acetal. ’ Dl;$cid 8 was also directly available in good eaction of 2 equiv of dilithio acetate with 1,4-dibromo-trans-2-butene (2 hr at
References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
11. 12. 13. 14. 15.
and Notes
E. J. Corey and H. L. Pearce, J. Am. Chem. Sot., s, 5841 (1979). K. Alder and S. Schneider, Liebigs Ann. Chem., 524, 189 (1936). Several equivalents of pyridine may be added to solubilize the diacid. M. Kate, M. Kageyama, R. Tanaka, K. Kuwahara, and A. Yoshikoshi, J. Org. Chem., 40, 1932(1975). Satisfactory infrared, proton magnetic resonance and mass spectrawereobtainedforeachcompound. Lead tetraacetate used in Chis work was recyrstallized from acetic acid and freed of solvent in vacua. H. E. Holmquist, F. D. Marsh. J. C. Sauer, and V. A. Engelhardt, J.Am. Chem.Soc.,g, 3681 (1959). 0. Diels and K. Alder, Liebigs Ann. Chem., 9, 98 (1928). T. Ogino and K. Mochizuki, Chem. Lett., 443 (1979). P. G. Gassman and X. Creary, Chem. Commun., 1214 (1972). (a) J. Nagarkatti and K. Ashley, Tetrahedron Letters, 4599 (1973); (b) G. Pollini, R. Tadia, A. Barco, J. Benetti, Org. Prep. and Proc. Int., 5, 217 (1974). (a) S. Hanessian, A. Bargiotti, and M. LaRue, Tetrahedron Letters, 737 (1978); Pura,TetrahedronLetters, 5223 (1970). (b) F. W. Eastwood, K. J. Harrington, T. S. JosanandJ.~. P. L. Creger, J. Org. Chem., 37, 1907 (1972). For studies of acetoxy lactonization of unsaturated carboxylic acids see, R. M. Moriarty, H. G. Walsh and H. Gopal, Tetrahedron Letters, 4363, 4369 (1966). This research was assisted financially by the National Science Foundation.
(Received
in USA 4 February
1980)