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Chiral induction in a biomimetic olefin cyclization
Tetrahedron Letters,Vol.30,No.l7,pp Printed in Great Britain
0040-4039/89 $3.00 Pergamon Press plc
2267-2268,1989
CHIRAL INDUCTION INA BIOMIMETICOLEFIN
EideyukiTa%enaka.'Tomoh~Sato,'
Facu1t.y ofPharmaceutical
Sciences, Tokushima
Japan,+ShionogiResearch
derivatives products
in maximum 76% diastereomeric are established
Although cyclization though
a few
mercury(U)
procedures
Herein
tion of perillene Chiral and
Yamamoto’s equiv)
number
carbocycles,
acetals
of studies
been
conlples,3
described
derivati\Tes 2a-2f
subsequent procedure.6
’ in dichloromathar@
andMugioNishizawa*
Bunri
Univer-sjty, J'amashiro-Cho,
have
applied
from
with
dimethyl
it
of a chiral
perillene
of the predominant
with the biomimetic
a remaining
problem
an effective
synthesis
induction
770,
transformations.
developed
to the
chiral
of chiral
prepared
cyclization
out dealing
is still
We have
is an effective
acetalization When
been carried
Tokushjma
Osaka 553,Japan
configuration
and chemical
induction
reported.2 and
a biomimetic
The absolute
study
chiral
wit.h a variety were
during
excess.
diffraction
effective
have
triflate/amine
terpenoids.“B5
CH&l,)
by X-ray
a large
into
CYCLIZATION
Institute, Shionogi & Co.Ltd.,Fukushimaku,
Abstract: Chiral induction has been achieved
+ .oo
of
in this
cyclization
a variety
olefin field, agent,
of polycychc
(up to 76% de) during
the cycliza-
acetals. perillene
optically
tartarate
at -78 “C for 3 h, a clean
2267
(1) via oxidation
active
tartaric
derivative cyclization
2a
acid was
(SeOJtert-C,H,OOH/
derivatives
treated
according
with
took place to give
an
Hg(OTf)?
to (1.2
organomer-
2268
curie
product
ing material
in 44% .yield after (36%).
and aaa. These
and dichloromethane
under
other
the
summarized this
cyclization
nalysis
CH,Cl,) reduction diol acetal
Alkyl
the
absolute
5, [n],”
6 was tosylated
we have
metic olefin
into
revealed the
that
neighboring
are
and
carbons
high
HglOTf),
4b-f
reduced
acetals
3a
(4.6 x 250
from
hexane
wags.
were
3a-3d
cases.
converted
originated
The absolute
crystal
into
the
prepared
by LiAlH_, reduction
reflux
from
as
during
X ray aidentical
(NaBH,/NaOH/C,H,OH/
(c 1.26, CHCl,),
(LiAlH,,
respectively,
recognition
Single
demercuration
-2.9”
in dichloromethane
in the latter
with that derived
within
column
(minor),
diastereoface
with a sample obtained
then
the chiral
with and
better
by reductive
was identified
of diastereoisomers
3a was crystallized
by the following
A diol 6, talD ”
start-
t8.3” (c 2.37, CHCl,).
treated
rather
In turn,
3a.
3f, was identical
isomer
3b-f (major)
yields
(c 1.22, CHCl,),
(TsCl/Pyridine)
also
was established
(CH,N,).
7, lalD I5 +13.Fj” (c 0.39, CHCl,),
major
gave
2a-2d
structure
-18.6’
of dibenzylether
Thus
to afford
tartarates
products
re-esterification
configurations
Table _I__.
as above
with the recovered
HPLC LYMC-D-SIL-5
mp 112 “C, [al,“O
Zb-2f were
than 2e and Zf, but chemical
ester and
needles,
along
to be a 88:12 mixture
by preparative
The resulting
colorless
conditions I.
(5:l)l.
chromatography
this product
separated
derivatives
of the major
revealed
dimethyl
to give
in Table
configuration
were
acetate
tartarate
same
gel column
HPLC and NMR showed
diastereomers
mml, henane and ethyl
The
silica
in dioxane).
by Li/NH, of 5.
The
The resulting
from 3a. L-It)-tartaric
16-76% diastereomeric
excess
acid induce during
R
a biomi-
cyclization.
1. Hg(OTf),
induced cyclization _____~_._~
olefin
of perillene
3/4 ratio
2a 2b 2c 2d 2a Rf
derivatives.
yield
88:12 87:13 85:I5 80:20 70:30 58:42
(%l -~-
44 51 46 44 53 71
PLUTO Drawing of 3a REFERENCES I. On leave from Shionogi Aburahi Laboratories, Shionogi & CO., Ltd.. 2. S. Yamada, M. Shibasaki, and S. Terashima, Tetrahedron Lett., 1973, 381. M. Shibasaki, S. Terashima, and S. Yamada, Chem. Charm, Bull.,1975, 2.Y,279. W. S. Johnson, C. A. Harbert, 8. E. Ratcliffe, and R. D. Stipanovic, J. Am. Chem. Sot., 1976, 98, 6188. G. Demailly and G. Solladie, J. 131-g.C&m., 1983, 46, 3102. S. Sakane, J. Fujiwara, K. Maruoka, and H. Yamamoto, J. Am. Chem. Sot., 1983, 105, 6154. 3. M. Nishizawa, H. Takenaka, H. Nishide, and Y, Hayashi, Tetrahedron Lert., 1983, 24, 2581. 4. M. Nishizawa, H. Takenaka, and Y. Hayashi, J. Org. Chem., 1986, 51, 806. 5. M. Nishizawa, H. Yamada, and Y. Hayashi, J. Org. Chem., 1987, 52, 4878. 6. A. Mori, I. Arai, H. Yamamoto, H. Nakai, and Y. Arai, Tetrahedron, 1986, 23, 6447. 7. Acetals 2a-2f did not react with Hg(OTf),/amine complex at all, 8. For the cyclization at low temperature, dichloromethane was found to be superior than nitromethane used commonly. 9. Crystal data of 3a: C 1oH,.ClOTHg, M 559.4, I??,, a = 10.540(l), b q 14.575(2), c = 6.013(l) A, fi = 90.80(l)” , V = 923.712) A”, 2 = 2. Final residual R 0.048 and & 0.058. Final atomic co-ordinates have been deposited at the Cambridge Crystallographic Data Centre. (Received
in
Japan
1 March
1989)
0040-4039/89 $3.00 Pergamon Press plc
2267-2268,1989
CHIRAL INDUCTION INA BIOMIMETICOLEFIN
EideyukiTa%enaka.'Tomoh~Sato,'
Facu1t.y ofPharmaceutical
Sciences, Tokushima
Japan,+ShionogiResearch
derivatives products
in maximum 76% diastereomeric are established
Although cyclization though
a few
mercury(U)
procedures
Herein
tion of perillene Chiral and
Yamamoto’s equiv)
number
carbocycles,
acetals
of studies
been
conlples,3
described
derivati\Tes 2a-2f
subsequent procedure.6
’ in dichloromathar@
andMugioNishizawa*
Bunri
Univer-sjty, J'amashiro-Cho,
have
applied
from
with
dimethyl
it
of a chiral
perillene
of the predominant
with the biomimetic
a remaining
problem
an effective
synthesis
induction
770,
transformations.
developed
to the
chiral
of chiral
prepared
cyclization
out dealing
is still
We have
is an effective
acetalization When
been carried
Tokushjma
Osaka 553,Japan
configuration
and chemical
induction
reported.2 and
a biomimetic
The absolute
study
chiral
wit.h a variety were
during
excess.
diffraction
effective
have
triflate/amine
terpenoids.“B5
CH&l,)
by X-ray
a large
into
CYCLIZATION
Institute, Shionogi & Co.Ltd.,Fukushimaku,
Abstract: Chiral induction has been achieved
+ .oo
of
in this
cyclization
a variety
olefin field, agent,
of polycychc
(up to 76% de) during
the cycliza-
acetals. perillene
optically
tartarate
at -78 “C for 3 h, a clean
2267
(1) via oxidation
active
tartaric
derivative cyclization
2a
acid was
(SeOJtert-C,H,OOH/
derivatives
treated
according
with
took place to give
an
Hg(OTf)?
to (1.2
organomer-
2268
curie
product
ing material
in 44% .yield after (36%).
and aaa. These
and dichloromethane
under
other
the
summarized this
cyclization
nalysis
CH,Cl,) reduction diol acetal
Alkyl
the
absolute
5, [n],”
6 was tosylated
we have
metic olefin
into
revealed the
that
neighboring
are
and
carbons
high
HglOTf),
4b-f
reduced
acetals
3a
(4.6 x 250
from
hexane
wags.
were
3a-3d
cases.
converted
originated
The absolute
crystal
into
the
prepared
by LiAlH_, reduction
reflux
from
as
during
X ray aidentical
(NaBH,/NaOH/C,H,OH/
(c 1.26, CHCl,),
(LiAlH,,
respectively,
recognition
Single
demercuration
-2.9”
in dichloromethane
in the latter
with that derived
within
column
(minor),
diastereoface
with a sample obtained
then
the chiral
with and
better
by reductive
was identified
of diastereoisomers
3a was crystallized
by the following
A diol 6, talD ”
start-
t8.3” (c 2.37, CHCl,).
treated
rather
In turn,
3a.
3f, was identical
isomer
3b-f (major)
yields
(c 1.22, CHCl,),
(TsCl/Pyridine)
also
was established
(CH,N,).
7, lalD I5 +13.Fj” (c 0.39, CHCl,),
major
gave
2a-2d
structure
-18.6’
of dibenzylether
Thus
to afford
tartarates
products
re-esterification
configurations
Table _I__.
as above
with the recovered
HPLC LYMC-D-SIL-5
mp 112 “C, [al,“O
Zb-2f were
than 2e and Zf, but chemical
ester and
needles,
along
to be a 88:12 mixture
by preparative
The resulting
colorless
conditions I.
(5:l)l.
chromatography
this product
separated
derivatives
of the major
revealed
dimethyl
to give
in Table
configuration
were
acetate
tartarate
same
gel column
HPLC and NMR showed
diastereomers
mml, henane and ethyl
The
silica
in dioxane).
by Li/NH, of 5.
The
The resulting
from 3a. L-It)-tartaric
16-76% diastereomeric
excess
acid induce during
R
a biomi-
cyclization.
1. Hg(OTf),
induced cyclization _____~_._~
olefin
of perillene
3/4 ratio
2a 2b 2c 2d 2a Rf
derivatives.
yield
88:12 87:13 85:I5 80:20 70:30 58:42
(%l -~-
44 51 46 44 53 71
PLUTO Drawing of 3a REFERENCES I. On leave from Shionogi Aburahi Laboratories, Shionogi & CO., Ltd.. 2. S. Yamada, M. Shibasaki, and S. Terashima, Tetrahedron Lett., 1973, 381. M. Shibasaki, S. Terashima, and S. Yamada, Chem. Charm, Bull.,1975, 2.Y,279. W. S. Johnson, C. A. Harbert, 8. E. Ratcliffe, and R. D. Stipanovic, J. Am. Chem. Sot., 1976, 98, 6188. G. Demailly and G. Solladie, J. 131-g.C&m., 1983, 46, 3102. S. Sakane, J. Fujiwara, K. Maruoka, and H. Yamamoto, J. Am. Chem. Sot., 1983, 105, 6154. 3. M. Nishizawa, H. Takenaka, H. Nishide, and Y, Hayashi, Tetrahedron Lert., 1983, 24, 2581. 4. M. Nishizawa, H. Takenaka, and Y. Hayashi, J. Org. Chem., 1986, 51, 806. 5. M. Nishizawa, H. Yamada, and Y. Hayashi, J. Org. Chem., 1987, 52, 4878. 6. A. Mori, I. Arai, H. Yamamoto, H. Nakai, and Y. Arai, Tetrahedron, 1986, 23, 6447. 7. Acetals 2a-2f did not react with Hg(OTf),/amine complex at all, 8. For the cyclization at low temperature, dichloromethane was found to be superior than nitromethane used commonly. 9. Crystal data of 3a: C 1oH,.ClOTHg, M 559.4, I??,, a = 10.540(l), b q 14.575(2), c = 6.013(l) A, fi = 90.80(l)” , V = 923.712) A”, 2 = 2. Final residual R 0.048 and & 0.058. Final atomic co-ordinates have been deposited at the Cambridge Crystallographic Data Centre. (Received
in
Japan
1 March
1989)