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Phenylselenenyl chloride as a reagent for the facile preparation of cyclic ethers from diolefins
TetrahedronLettersVol. 22, pp 1533 - 1536 @ Per@m,n Press Ltd. 3980. Printed in Great Britain
PH~NYLS~LENENY~
CHLORIDE AS A _RRAGENT FOR THE FACILE
PREPARATION OF CYCLIC ETHERS FROM DIOLEFINS
Sakae Uemura,
*
Akio Toshimitsu, Toshiaki Aoai, and Masaya Okano
Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan Summary: Various cyclic ethers are prepared in good to excellent yields by treating diolefins with phenylselenenyl acetonitrile.
chloride in aqueous
This is the most facile method for organoselenium-induced
formation of cyclic ethers from diolefins so far reported. We have recently reported that the treatment of diolefins with phenyl selenocyanate and copper{II) chloride in hydroxylic solvents resulted in the formation of cyclic ethers containing two phenylseleno groups. 1,2 et al.. have also reported similar cyclization
Nicolaou
reaction by using N-phenylseleno-
phthalimide, N-phenyl.selenosuccinimide, or "PhSeOH". 3,4
Although these methods
are very efficient for the preparation of cyclic ethers, it is still necessary to use the catalyst such as metal salt or acid, to carry out the reaction under anhydrous condition under argon, and/or to prepare effective phenylselenenyl reagents from various selenium compounds.
During the attempts to overcome
these disadvantages we have now found that the reaction of diolefins with commercially available phenylselenenyl
chloride in aqueous acetonitrile afforded similar
products in good to excellent yields. the use of phenylselenenyl
This seems to be the first example for
chloride in aqueous solvent.
This reagent has so far
been known to be very hygroscopic and therefore believed to be unstable in water. A typical experimental
phenylselenenyl
procedure is
as
follows.
To a solution of
chloride(l0 mmol) in aqueous acetonitrile(MeCN:H20=5:l,
was added l,+hexadiene(5
18 ml)
mmol) and the mixture was stirred at 76“C for 5 h,
After quenching the reaction by the addition of aqueous NaHC03, the mixture was extracted with chloroform and the extract was washed with aq. NaCl and dried over MgSO*.
Chloroform was then removed and the residue was subjected to
1534
column chromatography(silica-gel;
hexane-ethyl
acetate as eluent) to afford
a mixture of 2,5-bis(phenylselenomethyl)-1-oxacyclopentane selenomethyl-5-phenylseleno-1-oxacyclohexane (See Table).
(2) and 2-phenyl-
(2') in 90% yield[(ZJ):(2')=90:10]
The reactions of other several diolefins were similarly carried
out to give the corresponding cyclic ethers,
(l)-(9'), in comparable or better x x
l-4
yields to or than those reported. The structure of these products was 13 1 C- and H-NMR, IR, and mass spectra, and elemental analysis, the determined by isomer ratio being determined by liquid chromatography x 30 cm).
13C-NMR spectra and liquid chromatography
(column; p-Porasil 3.9 mm revealed that each of (l),
and (7) consisted of nearly equal amounts of two stereoisomers, (2), (5), (6), _ probably cis and trans with respect to two phenylselenomethyl one phenylselenomethyl
substituents or
and one phenylseleno moiety.
From diethyl diallylmalonate
a good yield of Spiro-bislactone
obtained together with the expected cyclic ether
(4) was
It was revealed by
(3). ^.
0
0
PhSeCl .
+
aq. MeCN
PhSe
SePh
(3)
13C-NMR spectra that (3) and (4) consisted of two stereoisomers(ca. three isomers(ca. 2:3:5), respectively. no isomerization between ditions,
Since we confirmed separately that
(3) and (4) occurred under the present reaction con-
(3) and (4) should be formed in different routes.
selenium-induced
3:l) and
intramolecular
Although organo-
lactonization of olefinic carboxylic acid has
5 been known, the present result seems to be the first example for such phenylselenolactonization
from carboxylic ester.
of ester to give a free dicarboxylic
The scheme such as the hydrolysis
acid which is followed by lactonization
give (4) may be ruled out, since no hydrolyzed compound of (3) [mono- or dicarboxylic acid of (3)] was detected in the products.
to
TABLE
Several
Diolefin
cyclic
Temp.
Time
("Cl
(h)
76
5
If-l
ethers
of diolefins a)
by oxyselenation
Products
Yielcl(X)b) (Product
PhSe
l/n
ratio)b)
SePh 5oc)
0
(1) 5
76
Ph5eaePh
+
PhSeaSeph
(2) EtO2C
90
(9O:lO)
97
(42:58)c)
96
(50:50)')
(2’)
C02Et 5
76
(3) 25
5
76
5
+
($1
Y--k
n
34 SePh
4-O-L
76
24
66
(6)
Y/-“-L
76
24
55
PhSe(IkePh
(7) 5
CILY
,,,edseph
i
PhSe@SePh
76
(8)
76 25
a) Diolefin used.. ratio
(1 mmol), b) Determined
of the
isolated
PhSe+.., "C,, SePh
PhS&*"
PhSeCl
(2 mmol),
by liquid products.
(84:16)d)
94
(
92
(88:12)
(8')
24 24
70
+
h, $ePh
and aq.MeCN
chromatography. d) Assignment
(3.6 ml;
MeCN:H20
c) Isolated for two products
3:97)
= 5:l) were
yield might
and the be reversed
1536
Another ratio
of
interesting
(9) to
(9') from
solvent-controlled with
the
on the other changing
hand,
namically The
of
the
the reaction
the predominant
seems
The direct
moiety.
in situ,
v-i-aaddition
by hydrolysis,
cyclization addition
with
bond,
alcohol
in Table,
to give
however,
(9) or
(9') being
of another
acid(PhSeOH),
can not be ruled
by
(9') was
a thermody-
chloride
a fi-hydroxyselenide
participation
method,
simply
of phenylselenenyl
of phenylselenenic
to one double
or methyl
respectively,
the
(9') by oxyselenation
By the present
as shown
isomer
reported1
(9') can be controlled
namely,
to proceed
followed
undergoes
(9) or
in the
already
(9) or
tetrahydrofuran
at 25°C or 76OC,
reaction
subsequently
of
is found
We have
(9'), respectively.
temperature;
product.
method
of either
i..e., aqueous (9) or
product
bond,
formation
formation
stable
one double
formed
system:
formation
of the present
i,5-cyclooctadiene.
selective
PhSeCN/CuC12
prefers
feature
to
which
phenylseleno
which out
may
be
as the first
step.
Acknowledgement.
We thank
Dr. T. Mitsudo
of Kyoto
University
for
13C-N!4R
J. C. S. Chem.
Commun.,
measurement.
References 1. s. Uemura,
A. Toshimitsu,
T. Aoai,
and ?I. Okano,
A. Toshimitsu,
T. Aoai,
and M. Okano,
610(1979). 2. S. Uemura,
3. K. C. Nicolaou,
-*sot 4.
r 101,
D. A. Claremon,
Chem.,
5. K. C. Nicolaou Clive
Chem. and
Lett.,
1359(1979).
S. P. Seitz,
J. Am.
Chem
3704(1979).
R. M. Scarborough, J. Orq.
W. E. Barnette,
Jr.,
A. B. Smith
z,
1742(1979).
and
2. Lysenko,
and G. Chittattu,
III, IV, E. Barnette,
J. Am. Chem.
J. C. S. Chem.
(Received in Japan 25 January 1980)
Sot:, 2,
Commun.,
and K, C. Nicolaou,
3185(1977);
484(1977).
D. L. J.
PH~NYLS~LENENY~
CHLORIDE AS A _RRAGENT FOR THE FACILE
PREPARATION OF CYCLIC ETHERS FROM DIOLEFINS
Sakae Uemura,
*
Akio Toshimitsu, Toshiaki Aoai, and Masaya Okano
Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan Summary: Various cyclic ethers are prepared in good to excellent yields by treating diolefins with phenylselenenyl acetonitrile.
chloride in aqueous
This is the most facile method for organoselenium-induced
formation of cyclic ethers from diolefins so far reported. We have recently reported that the treatment of diolefins with phenyl selenocyanate and copper{II) chloride in hydroxylic solvents resulted in the formation of cyclic ethers containing two phenylseleno groups. 1,2 et al.. have also reported similar cyclization
Nicolaou
reaction by using N-phenylseleno-
phthalimide, N-phenyl.selenosuccinimide, or "PhSeOH". 3,4
Although these methods
are very efficient for the preparation of cyclic ethers, it is still necessary to use the catalyst such as metal salt or acid, to carry out the reaction under anhydrous condition under argon, and/or to prepare effective phenylselenenyl reagents from various selenium compounds.
During the attempts to overcome
these disadvantages we have now found that the reaction of diolefins with commercially available phenylselenenyl
chloride in aqueous acetonitrile afforded similar
products in good to excellent yields. the use of phenylselenenyl
This seems to be the first example for
chloride in aqueous solvent.
This reagent has so far
been known to be very hygroscopic and therefore believed to be unstable in water. A typical experimental
phenylselenenyl
procedure is
as
follows.
To a solution of
chloride(l0 mmol) in aqueous acetonitrile(MeCN:H20=5:l,
was added l,+hexadiene(5
18 ml)
mmol) and the mixture was stirred at 76“C for 5 h,
After quenching the reaction by the addition of aqueous NaHC03, the mixture was extracted with chloroform and the extract was washed with aq. NaCl and dried over MgSO*.
Chloroform was then removed and the residue was subjected to
1534
column chromatography(silica-gel;
hexane-ethyl
acetate as eluent) to afford
a mixture of 2,5-bis(phenylselenomethyl)-1-oxacyclopentane selenomethyl-5-phenylseleno-1-oxacyclohexane (See Table).
(2) and 2-phenyl-
(2') in 90% yield[(ZJ):(2')=90:10]
The reactions of other several diolefins were similarly carried
out to give the corresponding cyclic ethers,
(l)-(9'), in comparable or better x x
l-4
yields to or than those reported. The structure of these products was 13 1 C- and H-NMR, IR, and mass spectra, and elemental analysis, the determined by isomer ratio being determined by liquid chromatography x 30 cm).
13C-NMR spectra and liquid chromatography
(column; p-Porasil 3.9 mm revealed that each of (l),
and (7) consisted of nearly equal amounts of two stereoisomers, (2), (5), (6), _ probably cis and trans with respect to two phenylselenomethyl one phenylselenomethyl
substituents or
and one phenylseleno moiety.
From diethyl diallylmalonate
a good yield of Spiro-bislactone
obtained together with the expected cyclic ether
(4) was
It was revealed by
(3). ^.
0
0
PhSeCl .
+
aq. MeCN
PhSe
SePh
(3)
13C-NMR spectra that (3) and (4) consisted of two stereoisomers(ca. three isomers(ca. 2:3:5), respectively. no isomerization between ditions,
Since we confirmed separately that
(3) and (4) occurred under the present reaction con-
(3) and (4) should be formed in different routes.
selenium-induced
3:l) and
intramolecular
Although organo-
lactonization of olefinic carboxylic acid has
5 been known, the present result seems to be the first example for such phenylselenolactonization
from carboxylic ester.
of ester to give a free dicarboxylic
The scheme such as the hydrolysis
acid which is followed by lactonization
give (4) may be ruled out, since no hydrolyzed compound of (3) [mono- or dicarboxylic acid of (3)] was detected in the products.
to
TABLE
Several
Diolefin
cyclic
Temp.
Time
("Cl
(h)
76
5
If-l
ethers
of diolefins a)
by oxyselenation
Products
Yielcl(X)b) (Product
PhSe
l/n
ratio)b)
SePh 5oc)
0
(1) 5
76
Ph5eaePh
+
PhSeaSeph
(2) EtO2C
90
(9O:lO)
97
(42:58)c)
96
(50:50)')
(2’)
C02Et 5
76
(3) 25
5
76
5
+
($1
Y--k
n
34 SePh
4-O-L
76
24
66
(6)
Y/-“-L
76
24
55
PhSe(IkePh
(7) 5
CILY
,,,edseph
i
PhSe@SePh
76
(8)
76 25
a) Diolefin used.. ratio
(1 mmol), b) Determined
of the
isolated
PhSe+.., "C,, SePh
PhS&*"
PhSeCl
(2 mmol),
by liquid products.
(84:16)d)
94
(
92
(88:12)
(8')
24 24
70
+
h, $ePh
and aq.MeCN
chromatography. d) Assignment
(3.6 ml;
MeCN:H20
c) Isolated for two products
3:97)
= 5:l) were
yield might
and the be reversed
1536
Another ratio
of
interesting
(9) to
(9') from
solvent-controlled with
the
on the other changing
hand,
namically The
of
the
the reaction
the predominant
seems
The direct
moiety.
in situ,
v-i-aaddition
by hydrolysis,
cyclization addition
with
bond,
alcohol
in Table,
to give
however,
(9) or
(9') being
of another
acid(PhSeOH),
can not be ruled
by
(9') was
a thermody-
chloride
a fi-hydroxyselenide
participation
method,
simply
of phenylselenenyl
of phenylselenenic
to one double
or methyl
respectively,
the
(9') by oxyselenation
By the present
as shown
isomer
reported1
(9') can be controlled
namely,
to proceed
followed
undergoes
(9) or
in the
already
(9) or
tetrahydrofuran
at 25°C or 76OC,
reaction
subsequently
of
is found
We have
(9'), respectively.
temperature;
product.
method
of either
i..e., aqueous (9) or
product
bond,
formation
formation
stable
one double
formed
system:
formation
of the present
i,5-cyclooctadiene.
selective
PhSeCN/CuC12
prefers
feature
to
which
phenylseleno
which out
may
be
as the first
step.
Acknowledgement.
We thank
Dr. T. Mitsudo
of Kyoto
University
for
13C-N!4R
J. C. S. Chem.
Commun.,
measurement.
References 1. s. Uemura,
A. Toshimitsu,
T. Aoai,
and ?I. Okano,
A. Toshimitsu,
T. Aoai,
and M. Okano,
610(1979). 2. S. Uemura,
3. K. C. Nicolaou,
-*sot 4.
r 101,
D. A. Claremon,
Chem.,
5. K. C. Nicolaou Clive
Chem. and
Lett.,
1359(1979).
S. P. Seitz,
J. Am.
Chem
3704(1979).
R. M. Scarborough, J. Orq.
W. E. Barnette,
Jr.,
A. B. Smith
z,
1742(1979).
and
2. Lysenko,
and G. Chittattu,
III, IV, E. Barnette,
J. Am. Chem.
J. C. S. Chem.
(Received in Japan 25 January 1980)
Sot:, 2,
Commun.,
and K, C. Nicolaou,
3185(1977);
484(1977).
D. L. J.