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Synthetic routes to cyclopropylidenecarbinols and to cyclopropylidienes
Tetrahedron Letters, Vo1.22, Printed in Great Britain
No.22,
pp
0040-4039/81/222135-04$02.00/O 01981 Pergamon Press Ltd.
2135 - 2138, 1981
SYNTHETIC ROUTES TO CYCLOPROPYLIDENECARBINOLSAND TO CYCLOPROPYLIDIENES
S. Halazy
and A. Krief"
Facult6s
Universitaires Notre-Dame de la Paix Department of Chemistry Namur (Belgium) 61, rue de Bruxelles, B-5000
FuncXionaLized atky.Lidux cy&o)3hopanu have been phepated Ahorn l-be&no l-v&L cyctoptopanti u&&g [2,3] nigmaa%opic h.eahhangemeti 06 theA cotlhebponding be,&A comption uLth nutphuh anaLoguen & ptenented. notiden OJL~e&nonium y&den.
In previous
, we have presented
In this letter, we disclose
propanes.
their conversion lability
1
papers
to selenium
open a new dimension
This paper deals with -2 and selenonium
I.
propanes
four synthetic
our first results
free derivatives. to the chemistry
the thermal
The variety
available
to I-seleno-l-vinyl their reactivity
of compounds
of cyclopropyl
and base induced
ylides -4 both readily
routes
concerning
prepared
cyclo-
namely
and their avai-
compounds.
rearrangement
respectively
from the corresponding
of selenoxides
l-seleno-l-vinylcyclo-
_l_
SCHEME1 OH
d RnR 3
RI R2 R3
2
-2
RAR 3
R&ii-:HR,
2
DC/R,
1
-
RnR a
2
-4 The
[2,3] sigmatropic
cohols readily methanol, usually
occurs20n
of straight
chain ally1 phenylselenoxides
to ally1 al-
treatment of ally1 phenylselenides with hydrogen peroxide[(THF/H20 or 2a 3 andismuch easier than the one performed on thio analogues which
20') (method A)]
requires
a thiophilic
In the course rearrange
rearrangement
agent.
of this study, we found that methylseleno
under similar
conditions
(method A). The rearranged
2135
analogues aremuchmoredifficult
to
alcohol 1 (Scheme II) was however
2136
formed in high yield when pyridine is present in the medium
(H202, 5 eq., pyridine 2 eq.,
CH2C12, 20') (method B)2bor when the reaction is performed with NaI04 (1,05 eq) in methanol/ water at ZO", 3h (method C). SCHEME II OH C6H,3 -CH =CH -CH2SeR -C6H13
-h-CH=CH2
-6
7
R=CH3
Method A
28%
R=CH3
Method B
84%
R =c6H5
Method C
84%
R=CH3
Method C
82%
Phenylseleno- and methylseleno derivatives 1 are, as it can be expected, much reluctant to rearrange probably due to the strain introduced in the transition state and in the alkylidene cyclopropanes2.
No ally1 alcohol was found under conditions A-C, but in the last case, the
corresponding selenoxides -2 are quantitatively extracted with chloroform after 3 hrs reaction. The desired transformation1 +fz '2 was successfully achieved by simply reacting the phenylselenoxides 1 (ZOO, 20h) with piperidine (5 eq) as selenophilic agent in a solvent of low polarity 4 (cyclohexane) (method D).SeetahleI.Neither the corresponding methylselenoxides,nor the phenylsulphoxidesanalogues 5 of _2 rearrange under similar conditions 6. TABLE I
JR1
-1
W D=
.R2 R3
-
(CHZ)~-
Method
R HO I3 I 91 C_C,R
2
2.
Yield in 2 (X)
H
C then D
75
H
C then D
70
H
C then D
75
H
C then D
807
H
C then D
77
'gH13 H
C then D
92
'gH13 H
A
0
B
33
C then D
The cyclopropylidenecarbinols 2 have been previously prepared by Conia method appears to successfully compete with the published ones.
16 7 and Bertrand 8. Our
2137
We further turned our attention towards a cloaely9relatedreaction which involves the [2,3 ] eigmatropic rearrangement of allylic aelenonium ylidea
and the application of the rearrangement
to cyclopropyl derivatives : this should produce functionalizedalkylidenecyclopropanea2. 10
Closely related rearrangements have been described in the case of allylic aulphur ylidea
;
nevertheless they have never been applied to the synthesis of alkylidenecyclopropanea. The aelenonium and aulphonium salts have been easily prepared by alkylation of the correaponding I-aeleno-l-vinylcyclopropanea1 or I-thio-l-vinylcyclopropanea 5 [CH3S03F in ether, (method E) or in dichloromethane (method F) or alkyliodide/AgBFbin dichloromethane (method G)] and lead to the rearranged alkylidenecyclopropaneaon reaction with base [t-BuOK, DMSO, 20',15 hra (method H)]; see table II. TABLE II RX-CH-R4 ~/RI C"-c \R2
XR C"==C
/RI
*
'R2 X
R
RI
Se
C"3
H
Se
C"3
H
Se
'6"5
Se Se Se S S
D== R2 '6"13 '6"13 H
H H'
'6"5
'6"13
H
'6"5
'6"13
C"3 H
C"3 '6"5
'6"13
%
E then H
H
a5
H
53
G(CH31)then H
H
60
G(CH31)then H
H
56
F then H
H
67
E then H
H
85 71
C"3 H
G(CH31)then H
'6"13
Yields (%)
G(CH31)then H
G(EtI)then H
'6"13
H
'6"5
Methods
5 -
77
The homoallyl aelenides were found good precursors of dienea. Alkylation of the selenium atom (method E) followed by treatment with t-BuOK/DMSO (method H) regioaelectivelyproduces the dienea by an elimination reaction I1 (Scheme III). SCHEME III
CH3SeCH2-CH=CH-C
H E 613
H
F”2SeC”3 E
CH2 =C"-CH-C6H13
"
C"2 I CH2 =C" -C -C6H13
98%
71%
I
I
CH2SeCH3 E C"=C"C
H 6 13
D
E
=C"-C"C6H13
"
H85%
C"2
D
==-C"-CC-C~"~~ 90%
2138
To our knowledge, We are currently dienes
investigating
in Diels-Alder
1. a) S. Halazy, b) S. Halazy,
only one synthesis
of cyclopropylidiene
the scope of these reactions
has been so far described and the reactivity
12
.
of cyclopropyli-
reactions.
A. Krief, A. Krief,
Tet. Lett., Tet. Lett.,
in press. in press.
2. a) K.B. Sharpless, M.W. Young, R.F. Lauer, Tet. Lett., 1979 (1973). b) D.L.J. Clive, G. Chittattu, N.J. Curtis, S.M. Menchen, J.C.S. Chem. Carmn., 770 (1978). 3. a) D.E. Evans, G.C. Andrews, Act. of Chem. Res., 147 (1974). b) R.W. Hoffmann, Angew. Chem. Int. Ed., fi, 563 (1979). 4. Similar observations have already been made for ally1 sulphoxides J. Jacohas, E.G. Miller, K. Mislow, J. Amer. Chem. Sot., 90, 4869
: P. Bickart, F.W. Carson, (1968).
5. I-phenylthio-1-vinylcyclopropanes used in this study have been prepared from e-phenylthiomethods we discrihed for selenium cyclopropyllithium l3 using the regio and stereoselective analogues l.For other synthesis of such derivatives see B.M. Trost, D.E. Keeley, H.C. Arndt, M.J. Bogdanowicz, J. Amer. Chem. Sot., 99, 3088 (1977). 6. Analoguous sulphoxides have been described to remain unchanged on heating for two hours at 90°. M. Franck-Neumann, J.J. Lohmann, Angew. Chem. Int. Ed., 323 (1977). 7. G. Rousseau,
P. Le Perchec,
8. M. Bertrand,
R. Maurin,
J.M. Conia, Tetrahedron,
Bull. Sot. Chim. France,
2779
3475
(1978).
(1967).
9. K.B. Sharpless, R.M. Gordon, R.F. Lauer, D.W. Patrick, S.P. Singer, M.W. Young, Scripta, c, 9 (1975). P.G. Gassmann, T. Mura, A. Massman, J.C.S. Chem. Comm., 558 (1980).
Chemica
10. B.M. Trost, L.S. Melvin Jr., Sulfur Ylides (Organic Chemistry, 31),Academic Press, 1~9 1975. E. Block, Reactions of organosulfur compounds (Organic Chemistry 37),Academic Press,NY,l978. 11. S. Halazy,
A. Krief,
12. K. Kitatani,
Tet. Lett.,
T. Hiyama,
13. B.M. Trost, E.K. Keeley, 3080 (1977).
(Received
4233
H. Nozaki,
in UK 24 March
H.C. Arndt,
1981)
(1979).
J. Amer. Chem. Sot., 97, 949 (1975). J.H. Rigby, M.J. Bogdanowicz,
J. Amer.
Chem. Sot., 99,
No.22,
pp
0040-4039/81/222135-04$02.00/O 01981 Pergamon Press Ltd.
2135 - 2138, 1981
SYNTHETIC ROUTES TO CYCLOPROPYLIDENECARBINOLSAND TO CYCLOPROPYLIDIENES
S. Halazy
and A. Krief"
Facult6s
Universitaires Notre-Dame de la Paix Department of Chemistry Namur (Belgium) 61, rue de Bruxelles, B-5000
FuncXionaLized atky.Lidux cy&o)3hopanu have been phepated Ahorn l-be&no l-v&L cyctoptopanti u&&g [2,3] nigmaa%opic h.eahhangemeti 06 theA cotlhebponding be,&A comption uLth nutphuh anaLoguen & ptenented. notiden OJL~e&nonium y&den.
In previous
, we have presented
In this letter, we disclose
propanes.
their conversion lability
1
papers
to selenium
open a new dimension
This paper deals with -2 and selenonium
I.
propanes
four synthetic
our first results
free derivatives. to the chemistry
the thermal
The variety
available
to I-seleno-l-vinyl their reactivity
of compounds
of cyclopropyl
and base induced
ylides -4 both readily
routes
concerning
prepared
cyclo-
namely
and their avai-
compounds.
rearrangement
respectively
from the corresponding
of selenoxides
l-seleno-l-vinylcyclo-
_l_
SCHEME1 OH
d RnR 3
RI R2 R3
2
-2
RAR 3
R&ii-:HR,
2
DC/R,
1
-
RnR a
2
-4 The
[2,3] sigmatropic
cohols readily methanol, usually
occurs20n
of straight
chain ally1 phenylselenoxides
to ally1 al-
treatment of ally1 phenylselenides with hydrogen peroxide[(THF/H20 or 2a 3 andismuch easier than the one performed on thio analogues which
20') (method A)]
requires
a thiophilic
In the course rearrange
rearrangement
agent.
of this study, we found that methylseleno
under similar
conditions
(method A). The rearranged
2135
analogues aremuchmoredifficult
to
alcohol 1 (Scheme II) was however
2136
formed in high yield when pyridine is present in the medium
(H202, 5 eq., pyridine 2 eq.,
CH2C12, 20') (method B)2bor when the reaction is performed with NaI04 (1,05 eq) in methanol/ water at ZO", 3h (method C). SCHEME II OH C6H,3 -CH =CH -CH2SeR -C6H13
-h-CH=CH2
-6
7
R=CH3
Method A
28%
R=CH3
Method B
84%
R =c6H5
Method C
84%
R=CH3
Method C
82%
Phenylseleno- and methylseleno derivatives 1 are, as it can be expected, much reluctant to rearrange probably due to the strain introduced in the transition state and in the alkylidene cyclopropanes2.
No ally1 alcohol was found under conditions A-C, but in the last case, the
corresponding selenoxides -2 are quantitatively extracted with chloroform after 3 hrs reaction. The desired transformation1 +fz '2 was successfully achieved by simply reacting the phenylselenoxides 1 (ZOO, 20h) with piperidine (5 eq) as selenophilic agent in a solvent of low polarity 4 (cyclohexane) (method D).SeetahleI.Neither the corresponding methylselenoxides,nor the phenylsulphoxidesanalogues 5 of _2 rearrange under similar conditions 6. TABLE I
JR1
-1
W D=
.R2 R3
-
(CHZ)~-
Method
R HO I3 I 91 C_C,R
2
2.
Yield in 2 (X)
H
C then D
75
H
C then D
70
H
C then D
75
H
C then D
807
H
C then D
77
'gH13 H
C then D
92
'gH13 H
A
0
B
33
C then D
The cyclopropylidenecarbinols 2 have been previously prepared by Conia method appears to successfully compete with the published ones.
16 7 and Bertrand 8. Our
2137
We further turned our attention towards a cloaely9relatedreaction which involves the [2,3 ] eigmatropic rearrangement of allylic aelenonium ylidea
and the application of the rearrangement
to cyclopropyl derivatives : this should produce functionalizedalkylidenecyclopropanea2. 10
Closely related rearrangements have been described in the case of allylic aulphur ylidea
;
nevertheless they have never been applied to the synthesis of alkylidenecyclopropanea. The aelenonium and aulphonium salts have been easily prepared by alkylation of the correaponding I-aeleno-l-vinylcyclopropanea1 or I-thio-l-vinylcyclopropanea 5 [CH3S03F in ether, (method E) or in dichloromethane (method F) or alkyliodide/AgBFbin dichloromethane (method G)] and lead to the rearranged alkylidenecyclopropaneaon reaction with base [t-BuOK, DMSO, 20',15 hra (method H)]; see table II. TABLE II RX-CH-R4 ~/RI C"-c \R2
XR C"==C
/RI
*
'R2 X
R
RI
Se
C"3
H
Se
C"3
H
Se
'6"5
Se Se Se S S
D== R2 '6"13 '6"13 H
H H'
'6"5
'6"13
H
'6"5
'6"13
C"3 H
C"3 '6"5
'6"13
%
E then H
H
a5
H
53
G(CH31)then H
H
60
G(CH31)then H
H
56
F then H
H
67
E then H
H
85 71
C"3 H
G(CH31)then H
'6"13
Yields (%)
G(CH31)then H
G(EtI)then H
'6"13
H
'6"5
Methods
5 -
77
The homoallyl aelenides were found good precursors of dienea. Alkylation of the selenium atom (method E) followed by treatment with t-BuOK/DMSO (method H) regioaelectivelyproduces the dienea by an elimination reaction I1 (Scheme III). SCHEME III
CH3SeCH2-CH=CH-C
H E 613
H
F”2SeC”3 E
CH2 =C"-CH-C6H13
"
C"2 I CH2 =C" -C -C6H13
98%
71%
I
I
CH2SeCH3 E C"=C"C
H 6 13
D
E
=C"-C"C6H13
"
H85%
C"2
D
==-C"-CC-C~"~~ 90%
2138
To our knowledge, We are currently dienes
investigating
in Diels-Alder
1. a) S. Halazy, b) S. Halazy,
only one synthesis
of cyclopropylidiene
the scope of these reactions
has been so far described and the reactivity
12
.
of cyclopropyli-
reactions.
A. Krief, A. Krief,
Tet. Lett., Tet. Lett.,
in press. in press.
2. a) K.B. Sharpless, M.W. Young, R.F. Lauer, Tet. Lett., 1979 (1973). b) D.L.J. Clive, G. Chittattu, N.J. Curtis, S.M. Menchen, J.C.S. Chem. Carmn., 770 (1978). 3. a) D.E. Evans, G.C. Andrews, Act. of Chem. Res., 147 (1974). b) R.W. Hoffmann, Angew. Chem. Int. Ed., fi, 563 (1979). 4. Similar observations have already been made for ally1 sulphoxides J. Jacohas, E.G. Miller, K. Mislow, J. Amer. Chem. Sot., 90, 4869
: P. Bickart, F.W. Carson, (1968).
5. I-phenylthio-1-vinylcyclopropanes used in this study have been prepared from e-phenylthiomethods we discrihed for selenium cyclopropyllithium l3 using the regio and stereoselective analogues l.For other synthesis of such derivatives see B.M. Trost, D.E. Keeley, H.C. Arndt, M.J. Bogdanowicz, J. Amer. Chem. Sot., 99, 3088 (1977). 6. Analoguous sulphoxides have been described to remain unchanged on heating for two hours at 90°. M. Franck-Neumann, J.J. Lohmann, Angew. Chem. Int. Ed., 323 (1977). 7. G. Rousseau,
P. Le Perchec,
8. M. Bertrand,
R. Maurin,
J.M. Conia, Tetrahedron,
Bull. Sot. Chim. France,
2779
3475
(1978).
(1967).
9. K.B. Sharpless, R.M. Gordon, R.F. Lauer, D.W. Patrick, S.P. Singer, M.W. Young, Scripta, c, 9 (1975). P.G. Gassmann, T. Mura, A. Massman, J.C.S. Chem. Comm., 558 (1980).
Chemica
10. B.M. Trost, L.S. Melvin Jr., Sulfur Ylides (Organic Chemistry, 31),Academic Press, 1~9 1975. E. Block, Reactions of organosulfur compounds (Organic Chemistry 37),Academic Press,NY,l978. 11. S. Halazy,
A. Krief,
12. K. Kitatani,
Tet. Lett.,
T. Hiyama,
13. B.M. Trost, E.K. Keeley, 3080 (1977).
(Received
4233
H. Nozaki,
in UK 24 March
H.C. Arndt,
1981)
(1979).
J. Amer. Chem. Sot., 97, 949 (1975). J.H. Rigby, M.J. Bogdanowicz,
J. Amer.
Chem. Sot., 99,