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Synthesis with benzenesulfenyl chloride. A new way to cyclosativene
Tetrahedron LetLers idol. 31, PD 11707 - 0710 OPer@mon Press L?t-I.1980. Printed in Great
SYNTHESIS
WITH
Sritain
BENZENESULFEN~
CHLORIDE
A NEW WAY TO CYCLOSATIVENE
Denis HEISSLER(') Institut
BP 296/R8
The intricate (2) has attracted have been
molecular
structure
the attention
reported
and Jean-Jacques
de Chimie,
Universite
RIEHL
Louis Pasteur
- 67008 STRASSOURG
(FRANCE
)
of the tricyclene
related
sesquiterpene
of several
research
groups
and three syntheses
Tricyclene
A
c
recently
letter, we wish tetracyclic (Ph3P=CR2)
treatment and with
that functionalized
of benzenesulfenyl
to describe
methylketone followed
The starting available,
shown
addition
chosen
of the ditosylate cyanide
of this reaction
hydrogenation
(
for the synthesis
from cyclopentadiene -5 in HMPA, with
(IO equiv.,
120'0,
compounds
Ph
f! can be obtained by the (6) . In this 3
to the total
of 2 is the ditosylate
and citraconic
anhydrous
synthesis
of the
into cyclosativene by a Wittig (7) (Ph3P)3 RhCl, H2) .
lithium
12 h) afforded 4707
*Cl
to methylenenorbornenes
can be transformed
by a catalytic
material
in three steps,
sodium
an application
2, which
tricyclenic
chloride
I
&
=
We have
1
of this compound
so far(3-5).
Cyclosativenel_
eleetrophilic
cyclosativene
anhydride bromide
the nitrile
reaction
zwhich is readily (8) . Sequential
(6 equiv.,
12O"C, 4 h)
1, via the bromide
f~,
4708
in a one-pot
Reduction
equiv.,
of 8 with
was reduced
CH2C12,
0°C)
diisobutylalrinum
I h) followed by hydrolysis 2 which
The nitrile
(89 % yield).
chloride (')(I.1
sulfenyl yield.
procedure
(10 % aqueous
to compound
E
with
7 was
then allowed
to furnish
to react with benzene-
the tricyclenic
hydride (lo) (1.1 equiv.,
H2S04,
lithium
lO"C,
compound -8 in 85 X
benzene,
10°C * r.t.,
Ih) gave a 77 % yield of the aldehyde
triethylborohydride
('I) (6 equiv.,
THF,
r.t.,
18 h, 94 % yield). After
obtention
phenylthio
of the tricyclenic
substituent
after transformation of this latter would
yield
the skeleton
by treatment
with
by a Pinner
synthesis
It was assumed
sulfone 2,
suitable
of the expected
two carbon
B-keto
of its
that,
base
treatment
sulfone 14,
atoms necessary
sulfide -10 into the carbomethoxy acid
sulfone -Il. Mesylation
sodium
to take advantage
then serve
to complete
-2.
of -10 with m-chloroperbenzoic
of hydroxy
ketone 2,
group of this ketone -15 should
of the additional
compound
cyano sulfone -12 (88 % yield) yield)
cleavage
ketone -15. The carbonyl
of the hydroxy
yield
carbomethoxy
by reductive
for the introduction
Oxidation
quantitative followed
followed
of the target
The conversion as follows.
sulfide '0, we planned
of -10 into the tricyclic
compound
the tetracyclic
as a "handlen
bydroxy
to convert -10 into the tetracyclic
cyanide
sulfone -13 was
(2.2 equiv.,
of -11 (MsCl, NEt3,
(5 equiv.,
I:1 THF-DMSO,
carried
out
CH2C12)
gave a nearly (12) CH2C12, 0°C)
reflux,
16 h) led to the
which was transformed into the carbomethoxy sulfone -13 (87 % (13) (dry HCl, methanol, THF, O"C/ Ih , r.t./l h) followed by
an acid hydrolysis. Conversion
of the ci-alkylated carbomethoxy
sulfone 14 required
a Dieckmann
found that this condensation with
potassium
with
acetic
ketone
could be accomplished
(78%
The S-keto
yield).
(LiA1H4,
THF),
by treatment
reductive
13
by quenching
then transformed
cleavage
we
of compound
THF, r.t., 2 h) followed
sulfone -14 was
S-keto
into
(Li, EtNH2,
the
THF,
amalgam, (17). Use of other procedures (aluminum (IS, 19) proved unsatisfactory. Finally, (20, 21) followed by of -15 with methoxymethylenetriphenylphosphorane in DMSO
and oxidation
THF - water treatment
efficiently
(15) (5 equiv.,
bis(trimethylsilyl)amide
acid at -78°C
15 (71 % yield) by reduction
-780#V
hydrolysis produced
sulfone 13 into the desired tetracyclic (14) type condensation . After extensive investigation,
(Cr03-2py,
(35 % aqueous aldehyde
by oxidation
ACKNOWLEDGMENT
HC104,
ether,
-16 in 43 % yield.
(Cr03-Zpy),
NMR) as methylketone
to Professor
CH2C12)
or zinc dust, ethanol-acetic
acid)
45 min)
upon
we obtained
and epimerization
treatment
in 60 % yield,
(dry K2C03,
of -16 with methyllithium a ketone
which was
methanol, in ether
identified
3h) followed
(IR, 60 MHZ
(7) . -2
: We are very grateful A. Yoshikoshi
to Professor
for the IRand
J. Ficini
60 MHz NMR spectra
for a fruitful of ketones
discussion
-15 and 2
.
and
0
mn0 -@
18
-16 a) LiBr, WA,
1
12O'C ; b) NaCN, HMPA, 120°C (5 + 1 : 89 % yield) ; c) PhSC1,CH2C12,0"C (85 %)
d) (i-Bu)2 ALH, benzene
;
e)
IO % aqueous
H2SO,,(2 * 2 : 77 X) ; f) LiBHEt3, THF (94 %> ;
g) m-CPBA, CH2C12 (99 %) ; h) MsCl, NEt3, CH2C12 ; i) N&N,
THF, DMSO (11 ‘11. -
: 88 4)
;
j)
dry HCl, MeOH, THF ; k) H30+ (12 - + 13 : 87 X) ; 1) KN(SiMe3)2, THF (78 X) ; m) LiAlH&, THF ; n) Li, EtNH2, THF, -78°C ; O) CrO3-2py, CH2C12 (14 "2 : 71 %) ; p) Ph3P'CHOCH3, DMSO ; q) 35 % aqueous HC104, ether ; r) K2C03, McOH (2 + 16 : 43 X) ; s)MeLi, ether i t) Cr03-2py, CH2C12 (s+; : 60 %).
4710
REFERENCES AND NOTES
1) Centre National de la Recherche Scientifique. 2) L. SMEDMAN, E. ZAVARIN, Tetrahedron Lett. 3833 (1968) ; L.A. SMEDMAN, E. ZAVARIN, R. TERANISHI, Phytochemistry 8, 1457 (1969) 3) J.E. MC MURRY, Tetrahedron LeTt. 55 (1969) ; J.E. MC MLJRRY,.T.Org. Chem. =36, 2826 (1971) 3, 401 (1973) ; E. PIERS, R.W. BRITTON, 4) E. PIERS, M.B. GERAGHTY, M. SOUCY, Synth. Commun. = M.B. GERAGHTY, R.J. KEZIERE, R.D. SMILLIE, Can. J. Chem. g, 2827 (1975) ; E. PIERS, M.B. GERAGHTY, R.D. SMILLIE, M. SOUCY, Can. J. Chem. 2,
2849 (1975)
S.W. BALDWIN, J.C. TOMESCH, Tetrahedron Lett. 1055 (1975) ; S.W. BALDWIN, J.C. TOMESCH J. Org. Chem. z,
1455 (1980)
6) D. HEISSLER, J.J. RIEHL, Tetrahedron Lett. 3957 (1979); see also N.S. ZEFIROV, N.K. SADOVAJA, R.SH. ACHMEDOVA, X.V. BODRIKOV, Zh. Org. Khim. 15, 217
(1979); Chem.
Abst.90, 2036143 (1979) -= 7) F. KIW, R. SAKUMA, H. UDA, A. YOSHIKOSHI, Tetrahedron Lett. 3169 (1969) 81 D. HEISSLER, F. JUNG, J.P. VEVERT, J.J. RIEHL, Tetrahedron Lett. 4879 (1976) 9) Prepared according to F.G. BORDWELL; M. FIESER and L.F. FIESER,"Reagents for Organic Synthesis: Vol 5, p. 523, John Wiley and Sons, Inc.,New York (1975) L.I. ZAKHARKIN, I.M, KHORLINA, Dokl. Akad. Nauk
SSSR 116, 422 (1957) ; Chem. Abst. 52, -
804Of (1958) 95 1669 (1973) 11) B.C. BROWN, 5. KRISHNAMURTHY, J. Am. Chem. Sot. _I 12) R.K. CROSSLAND, K.L. SERVIS, J. Org. Chem. =35, 3195 (1970) 13) Reviews : - E.N. ZIL'BERMAN, Russ. Chem. Rev. =' 31 615 (1962) - P.L. COMFAGNON. M. MIOCQU!?,Ann.Chim. (Paris) 5, 23 (1970) 14) G. NEE, B. TCHOUBAR, Tetrahedron Lett. 3717 (197;) 151 Prepared according to C.A. BROWN, J. Org. Chem. =39, 3913 (1974) 16) W.E. TRUCE, D.P. TATE, D.N. BURDGE, J. Am. Chem. Sot. 82, 2872 (1960) 17) R. FtATCLIFFE,R. RODEHORST, J. Org. Chem. =35, 4000 (19;) 18) E.J. COREY, M. CHAYKOVSKY, J. Am. Chem. Sot. X7, 1345 (1965) 88=5498 (1966) 19) G.A. RUSSELL, G.J. MIKOL, J. Am. Chem. Sot. =' 20) S.G. LEVINE, J. Am. Chem. Sot. =80, 6150 (1958) 21) R. GREENWALD, M. CHAYKOVSKY, E.J. COREY, J. Org. Chem. =28, 1128 (1963) (Received in France 1 September 198O!
SYNTHESIS
WITH
Sritain
BENZENESULFEN~
CHLORIDE
A NEW WAY TO CYCLOSATIVENE
Denis HEISSLER(') Institut
BP 296/R8
The intricate (2) has attracted have been
molecular
structure
the attention
reported
and Jean-Jacques
de Chimie,
Universite
RIEHL
Louis Pasteur
- 67008 STRASSOURG
(FRANCE
)
of the tricyclene
related
sesquiterpene
of several
research
groups
and three syntheses
Tricyclene
A
c
recently
letter, we wish tetracyclic (Ph3P=CR2)
treatment and with
that functionalized
of benzenesulfenyl
to describe
methylketone followed
The starting available,
shown
addition
chosen
of the ditosylate cyanide
of this reaction
hydrogenation
(
for the synthesis
from cyclopentadiene -5 in HMPA, with
(IO equiv.,
120'0,
compounds
Ph
f! can be obtained by the (6) . In this 3
to the total
of 2 is the ditosylate
and citraconic
anhydrous
synthesis
of the
into cyclosativene by a Wittig (7) (Ph3P)3 RhCl, H2) .
lithium
12 h) afforded 4707
*Cl
to methylenenorbornenes
can be transformed
by a catalytic
material
in three steps,
sodium
an application
2, which
tricyclenic
chloride
I
&
=
We have
1
of this compound
so far(3-5).
Cyclosativenel_
eleetrophilic
cyclosativene
anhydride bromide
the nitrile
reaction
zwhich is readily (8) . Sequential
(6 equiv.,
12O"C, 4 h)
1, via the bromide
f~,
4708
in a one-pot
Reduction
equiv.,
of 8 with
was reduced
CH2C12,
0°C)
diisobutylalrinum
I h) followed by hydrolysis 2 which
The nitrile
(89 % yield).
chloride (')(I.1
sulfenyl yield.
procedure
(10 % aqueous
to compound
E
with
7 was
then allowed
to furnish
to react with benzene-
the tricyclenic
hydride (lo) (1.1 equiv.,
H2S04,
lithium
lO"C,
compound -8 in 85 X
benzene,
10°C * r.t.,
Ih) gave a 77 % yield of the aldehyde
triethylborohydride
('I) (6 equiv.,
THF,
r.t.,
18 h, 94 % yield). After
obtention
phenylthio
of the tricyclenic
substituent
after transformation of this latter would
yield
the skeleton
by treatment
with
by a Pinner
synthesis
It was assumed
sulfone 2,
suitable
of the expected
two carbon
B-keto
of its
that,
base
treatment
sulfone 14,
atoms necessary
sulfide -10 into the carbomethoxy acid
sulfone -Il. Mesylation
sodium
to take advantage
then serve
to complete
-2.
of -10 with m-chloroperbenzoic
of hydroxy
ketone 2,
group of this ketone -15 should
of the additional
compound
cyano sulfone -12 (88 % yield) yield)
cleavage
ketone -15. The carbonyl
of the hydroxy
yield
carbomethoxy
by reductive
for the introduction
Oxidation
quantitative followed
followed
of the target
The conversion as follows.
sulfide '0, we planned
of -10 into the tricyclic
compound
the tetracyclic
as a "handlen
bydroxy
to convert -10 into the tetracyclic
cyanide
sulfone -13 was
(2.2 equiv.,
of -11 (MsCl, NEt3,
(5 equiv.,
I:1 THF-DMSO,
carried
out
CH2C12)
gave a nearly (12) CH2C12, 0°C)
reflux,
16 h) led to the
which was transformed into the carbomethoxy sulfone -13 (87 % (13) (dry HCl, methanol, THF, O"C/ Ih , r.t./l h) followed by
an acid hydrolysis. Conversion
of the ci-alkylated carbomethoxy
sulfone 14 required
a Dieckmann
found that this condensation with
potassium
with
acetic
ketone
could be accomplished
(78%
The S-keto
yield).
(LiA1H4,
THF),
by treatment
reductive
13
by quenching
then transformed
cleavage
we
of compound
THF, r.t., 2 h) followed
sulfone -14 was
S-keto
into
(Li, EtNH2,
the
THF,
amalgam, (17). Use of other procedures (aluminum (IS, 19) proved unsatisfactory. Finally, (20, 21) followed by of -15 with methoxymethylenetriphenylphosphorane in DMSO
and oxidation
THF - water treatment
efficiently
(15) (5 equiv.,
bis(trimethylsilyl)amide
acid at -78°C
15 (71 % yield) by reduction
-780#V
hydrolysis produced
sulfone 13 into the desired tetracyclic (14) type condensation . After extensive investigation,
(Cr03-2py,
(35 % aqueous aldehyde
by oxidation
ACKNOWLEDGMENT
HC104,
ether,
-16 in 43 % yield.
(Cr03-Zpy),
NMR) as methylketone
to Professor
CH2C12)
or zinc dust, ethanol-acetic
acid)
45 min)
upon
we obtained
and epimerization
treatment
in 60 % yield,
(dry K2C03,
of -16 with methyllithium a ketone
which was
methanol, in ether
identified
3h) followed
(IR, 60 MHZ
(7) . -2
: We are very grateful A. Yoshikoshi
to Professor
for the IRand
J. Ficini
60 MHz NMR spectra
for a fruitful of ketones
discussion
-15 and 2
.
and
0
mn0 -@
18
-16 a) LiBr, WA,
1
12O'C ; b) NaCN, HMPA, 120°C (5 + 1 : 89 % yield) ; c) PhSC1,CH2C12,0"C (85 %)
d) (i-Bu)2 ALH, benzene
;
e)
IO % aqueous
H2SO,,(2 * 2 : 77 X) ; f) LiBHEt3, THF (94 %> ;
g) m-CPBA, CH2C12 (99 %) ; h) MsCl, NEt3, CH2C12 ; i) N&N,
THF, DMSO (11 ‘11. -
: 88 4)
;
j)
dry HCl, MeOH, THF ; k) H30+ (12 - + 13 : 87 X) ; 1) KN(SiMe3)2, THF (78 X) ; m) LiAlH&, THF ; n) Li, EtNH2, THF, -78°C ; O) CrO3-2py, CH2C12 (14 "2 : 71 %) ; p) Ph3P'CHOCH3, DMSO ; q) 35 % aqueous HC104, ether ; r) K2C03, McOH (2 + 16 : 43 X) ; s)MeLi, ether i t) Cr03-2py, CH2C12 (s+; : 60 %).
4710
REFERENCES AND NOTES
1) Centre National de la Recherche Scientifique. 2) L. SMEDMAN, E. ZAVARIN, Tetrahedron Lett. 3833 (1968) ; L.A. SMEDMAN, E. ZAVARIN, R. TERANISHI, Phytochemistry 8, 1457 (1969) 3) J.E. MC MURRY, Tetrahedron LeTt. 55 (1969) ; J.E. MC MLJRRY,.T.Org. Chem. =36, 2826 (1971) 3, 401 (1973) ; E. PIERS, R.W. BRITTON, 4) E. PIERS, M.B. GERAGHTY, M. SOUCY, Synth. Commun. = M.B. GERAGHTY, R.J. KEZIERE, R.D. SMILLIE, Can. J. Chem. g, 2827 (1975) ; E. PIERS, M.B. GERAGHTY, R.D. SMILLIE, M. SOUCY, Can. J. Chem. 2,
2849 (1975)
S.W. BALDWIN, J.C. TOMESCH, Tetrahedron Lett. 1055 (1975) ; S.W. BALDWIN, J.C. TOMESCH J. Org. Chem. z,
1455 (1980)
6) D. HEISSLER, J.J. RIEHL, Tetrahedron Lett. 3957 (1979); see also N.S. ZEFIROV, N.K. SADOVAJA, R.SH. ACHMEDOVA, X.V. BODRIKOV, Zh. Org. Khim. 15, 217
(1979); Chem.
Abst.90, 2036143 (1979) -= 7) F. KIW, R. SAKUMA, H. UDA, A. YOSHIKOSHI, Tetrahedron Lett. 3169 (1969) 81 D. HEISSLER, F. JUNG, J.P. VEVERT, J.J. RIEHL, Tetrahedron Lett. 4879 (1976) 9) Prepared according to F.G. BORDWELL; M. FIESER and L.F. FIESER,"Reagents for Organic Synthesis: Vol 5, p. 523, John Wiley and Sons, Inc.,New York (1975) L.I. ZAKHARKIN, I.M, KHORLINA, Dokl. Akad. Nauk
SSSR 116, 422 (1957) ; Chem. Abst. 52, -
804Of (1958) 95 1669 (1973) 11) B.C. BROWN, 5. KRISHNAMURTHY, J. Am. Chem. Sot. _I 12) R.K. CROSSLAND, K.L. SERVIS, J. Org. Chem. =35, 3195 (1970) 13) Reviews : - E.N. ZIL'BERMAN, Russ. Chem. Rev. =' 31 615 (1962) - P.L. COMFAGNON. M. MIOCQU!?,Ann.Chim. (Paris) 5, 23 (1970) 14) G. NEE, B. TCHOUBAR, Tetrahedron Lett. 3717 (197;) 151 Prepared according to C.A. BROWN, J. Org. Chem. =39, 3913 (1974) 16) W.E. TRUCE, D.P. TATE, D.N. BURDGE, J. Am. Chem. Sot. 82, 2872 (1960) 17) R. FtATCLIFFE,R. RODEHORST, J. Org. Chem. =35, 4000 (19;) 18) E.J. COREY, M. CHAYKOVSKY, J. Am. Chem. Sot. X7, 1345 (1965) 88=5498 (1966) 19) G.A. RUSSELL, G.J. MIKOL, J. Am. Chem. Sot. =' 20) S.G. LEVINE, J. Am. Chem. Sot. =80, 6150 (1958) 21) R. GREENWALD, M. CHAYKOVSKY, E.J. COREY, J. Org. Chem. =28, 1128 (1963) (Received in France 1 September 198O!