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Palladium-catalyzed reactions of alkenyloxiranes with carbon monoxide
Tetr&&onLatat. Vol. 34.No. 13.pi 21353138.1993 PMCdinGrutBriuin
oo4o-lo39/93s6.00+ .oa PquMnReuLId
Palladium-Catalyzed
Reactions of Alkenyloxiranes
with Carbon Monoxide
Isao Shimizu*,
Takashi Maruyama, Tozhiyuki
Makuta, and Akio Yamamoto*
Dcpamnent of AppliedChaaisrry,S&eel of Scbce andB@aeekg, Was&
University. 341 Ohkube.Shiijuku-ku. T&ye 169. Japan
Carbonylation of allylic compounds is a useful tool for organic synthesis. Allylic carbonates, halides, actra4Ls,~~~~.~~BSC~QJbc~~~~~~~~~~~~~n~~,~~ esters through pmce~ses pro&ding
via x-allylpalladium complexe@)-la)
Alkenybxbanes react with palladium
compoulids to give x-allylpalladim coniplexes, which undergo isomerization.2) nucleophilic reaction,31 or recbuckm.~However,
no c~%ony~a6w
0% aSxcny>oxllants promoltb
by p&Iai%um calaisysl has ken
We report here on the results of our kudy on the palladium-catalyzed reaction of alkenyloxiranes with carbon monoxide. The reaction course was found to vary depending on the nature of the alkenyloxiranes enp~i%urqqesofquuifcfs~-5in*~mi:
IZa~~~~M&qenuiiigontknatm~&fkau~~
of the alkenyloximne 1. l%GW@2 f-P@Et,NaB~ R2 llUk4CM&&l&
“1~
1
R’
R1wR2
EtOH. CO, r. t. 2
2135
4
2136
Reaction of isopmne monoxide la withCO (30 atm) in ethanol in the presence of Pda(C4H7)&12, iPr$W, NaBr, and maleic anhydride at room temperature for 12 h gave ethyl (E)-S-hydroxy-4-methyl-3pentenoate 2a in 86 96 yield after puriiication on column chromatography.tc) Similarly, (EWhydroxy-Sphenyl3pentenoate 2b was obtained in 69 96 yield by the carbonylation ofthe terminal alkenyloxirane lb (Scheme 2).
cl-
Yj&g$g$, +
EtOH +
CO
0
t&&c &xki& 86% 2a
la
lb
2b
Scheme 2
Carbonylation of alkenyloxiranes which have internal olefins (1, Ra=alkyl) also took place to give the corresponding hydroxy esters and B-Iactones but considerable amounts of 1.3-dienes were formed as shown in Table 1. The stemochemistty of the p-lactone 3c is assigned on the basis of the proton NMR spectrum where H. (8: 5.26 ) couples’ with Ht, (8: 4.89 ) with coupling of J=7.9 Hz, indicative of a cis relationship.
The
stereochemistry of the diene formed (4~) was (E , 2 ) as dipicted in Table 1. The (E)-olefii of the starting materials were inverted. But, the diene 4e obtained in the reaction of le with Co was a mixtum. Table 1 P&tiium-CtttalyA RUB
Alkalyloxime1
Reaction of Alkenyloxiraues with carboa Moxide Product(isolataiyield)
2137
The carbonylation of l&cyclohexadiet~ monoepoxi& 6 prczeeW stemoselcctively and gave a mixtum of hydroxy esters 7 and 8. But neither B-lactone nor 1.3~diene was formed in this case (Scheme 3).The e~o~y~~~~~~~~~~~~~~-~
3%rxWsA+Wz&n&*~ti~~~
proton NMR spectrum after hydrogenating 7 and 8 respectively. The stereochemistry of 8 indicates that the carbonylationpmceeds with inversion ofccnfiguration at the allylic carbon. wwI7w4
0
+
i-P@& NsBr maleic snbydfidc &OH
co (50 sun)
6
6 8
7 (7:8=9:5)
scheme 3
The mechanisms iUustratedin Scheme 4 are proposed to consistently Bccountfa the forma&n of ~lactone 3 am& i.Xitene SmSelectiVdy
4. Tne hng-qoeritng reactton 01 IllxenyloGnute 1 tifn p&&un in an sN2
XmNK%
to affcd
~-allylpalladium
CoYqdCX
converted into anti n-allylpahadium complex 10 by the n-o-n
9f)
The
Syn
c4uqnIex JWXC&~
~-~&fdhdim
ca@@eX
9 ii?
intetconversion. Coo&ration of CO to the
palladiumcomplexfollowedbyattackoftheoxideaniartothe~cOgiveofi~m~bes#i~cles 11 and 12 respectively. The ductive
elimination of palladium out of 11 affords Blactonc cis-3, whereas (E, Z)-
diene 4 is obtained by the decarboxylation from complex 12. The selectivity between reductive elimination and decarboxylation may depend on the stereochemistry of the in&mediate 11 or 12. However, stetwchemical requhements far these mactions am not obvious.
cis-3
R,/B/LRz
w(o)_
lZE)4
1 IE.E)
scheme4 Since the intramolecular participation of the oxide anion to CO coot&a&
to the palladium (11 or 12 in
Scheme 4) is impossible in the reaction of cyclii alkenyloxirane 6, neither Blactone nor diene was famed in this case. When alkenyloxirane IIhaving electron-withdrawing substituent Ra such as akoxycarbonyl group wem subjectcd to the reaction with CO, no car6onylatkm product was formed and allylic alcohol and diene were produced as reduction products of the oxirane (Scheme 5). The ratio of the allylic alcohol Sf to the diene 41 increased on decrease of the Co pressme employed. Indeed, aRylic alcoho1.W was obtained selectively at atmospheric a0 pressure. The presence of CO, however, is essential for reduction of If to 41 and Sf. When the reactionoflfwarcarriedoutintheabsenceof(?O,noreactian~andlfwas~~
2138
fI$$pg&; tideiiaahydkk
tB(30 run); MeOH r. t.
4f
7%
sf
67%
Schem 5 Although the role of CO and the precise mechanisms for the reduction am not known, involvement of an alkoxycarbonyl complex and its reaction with alcohol to give n-allylpalladium
hydride complex am probable.
Indeed, formation of dlethyl carbonate and dlethyl oxalate in the reaction of lg was continned by GC-mass specuoscopy (Scheme 6).
(EtO)&O + (CODBth
BtOH Scheme 6
This research was supported by the Grant-in-Aid from the Ministry of Education, Science and Culture (No 03233238 and No 04217235) and the Asahi Glass Foundation.
REFERENCES (a) J. Tsuji, K. Sate, .and H. Okumoto, J. Org. Chem., 49, 1341 (1984). (b) J. Kiji. T. Okano, W. 1. Nishiumi, and H. Konishi, Chem. La., 1988, 957. (c) S-I. Murahashi, Y. Imada, Y. TanQuchi, and S. H$shiura, Terruhedko~ Lerr., 29,494s (1988). (d) D. Neibecker, J. Poirler, and I. Tkatchenko, J. Org. Chem., 54.2459 (1989). 2. M. Suzuki, Y. Oda, and R. Noyori, J. Am. Chem. Sot., 101,1424(1979). B. M. Trost and G. A. Molar&r, 1. Am. Chem. Sot., 103,5969 (1981); J. Tsuji, H. Kataoka, and Y. 3. Kobaylishi, Terrahedren’E.ett., 22.2575 (1981). 4. M. Oshima, H. Yamaxakl, I. Shimizu, M. Nisar, and J. Tsuji. J. Am. Chem. Sot., 111.6280 (1989).
(Received in Japan 24 December 1992)
oo4o-lo39/93s6.00+ .oa PquMnReuLId
Palladium-Catalyzed
Reactions of Alkenyloxiranes
with Carbon Monoxide
Isao Shimizu*,
Takashi Maruyama, Tozhiyuki
Makuta, and Akio Yamamoto*
Dcpamnent of AppliedChaaisrry,S&eel of Scbce andB@aeekg, Was&
University. 341 Ohkube.Shiijuku-ku. T&ye 169. Japan
Carbonylation of allylic compounds is a useful tool for organic synthesis. Allylic carbonates, halides, actra4Ls,~~~~.~~BSC~QJbc~~~~~~~~~~~~~n~~,~~ esters through pmce~ses pro&ding
via x-allylpalladium complexe@)-la)
Alkenybxbanes react with palladium
compoulids to give x-allylpalladim coniplexes, which undergo isomerization.2) nucleophilic reaction,31 or recbuckm.~However,
no c~%ony~a6w
0% aSxcny>oxllants promoltb
by p&Iai%um calaisysl has ken
We report here on the results of our kudy on the palladium-catalyzed reaction of alkenyloxiranes with carbon monoxide. The reaction course was found to vary depending on the nature of the alkenyloxiranes enp~i%urqqesofquuifcfs~-5in*~mi:
IZa~~~~M&qenuiiigontknatm~&fkau~~
of the alkenyloximne 1. l%GW@2 f-P@Et,NaB~ R2 llUk4CM&&l&
“1~
1
R’
R1wR2
EtOH. CO, r. t. 2
2135
4
2136
Reaction of isopmne monoxide la withCO (30 atm) in ethanol in the presence of Pda(C4H7)&12, iPr$W, NaBr, and maleic anhydride at room temperature for 12 h gave ethyl (E)-S-hydroxy-4-methyl-3pentenoate 2a in 86 96 yield after puriiication on column chromatography.tc) Similarly, (EWhydroxy-Sphenyl3pentenoate 2b was obtained in 69 96 yield by the carbonylation ofthe terminal alkenyloxirane lb (Scheme 2).
cl-
Yj&g$g$, +
EtOH +
CO
0
t&&c &xki& 86% 2a
la
lb
2b
Scheme 2
Carbonylation of alkenyloxiranes which have internal olefins (1, Ra=alkyl) also took place to give the corresponding hydroxy esters and B-Iactones but considerable amounts of 1.3-dienes were formed as shown in Table 1. The stemochemistty of the p-lactone 3c is assigned on the basis of the proton NMR spectrum where H. (8: 5.26 ) couples’ with Ht, (8: 4.89 ) with coupling of J=7.9 Hz, indicative of a cis relationship.
The
stereochemistry of the diene formed (4~) was (E , 2 ) as dipicted in Table 1. The (E)-olefii of the starting materials were inverted. But, the diene 4e obtained in the reaction of le with Co was a mixtum. Table 1 P&tiium-CtttalyA RUB
Alkalyloxime1
Reaction of Alkenyloxiraues with carboa Moxide Product(isolataiyield)
2137
The carbonylation of l&cyclohexadiet~ monoepoxi& 6 prczeeW stemoselcctively and gave a mixtum of hydroxy esters 7 and 8. But neither B-lactone nor 1.3~diene was formed in this case (Scheme 3).The e~o~y~~~~~~~~~~~~~~-~
3%rxWsA+Wz&n&*~ti~~~
proton NMR spectrum after hydrogenating 7 and 8 respectively. The stereochemistry of 8 indicates that the carbonylationpmceeds with inversion ofccnfiguration at the allylic carbon. wwI7w4
0
+
i-P@& NsBr maleic snbydfidc &OH
co (50 sun)
6
6 8
7 (7:8=9:5)
scheme 3
The mechanisms iUustratedin Scheme 4 are proposed to consistently Bccountfa the forma&n of ~lactone 3 am& i.Xitene SmSelectiVdy
4. Tne hng-qoeritng reactton 01 IllxenyloGnute 1 tifn p&&un in an sN2
XmNK%
to affcd
~-allylpalladium
CoYqdCX
converted into anti n-allylpahadium complex 10 by the n-o-n
9f)
The
Syn
c4uqnIex JWXC&~
~-~&fdhdim
ca@@eX
9 ii?
intetconversion. Coo&ration of CO to the
palladiumcomplexfollowedbyattackoftheoxideaniartothe~cOgiveofi~m~bes#i~cles 11 and 12 respectively. The ductive
elimination of palladium out of 11 affords Blactonc cis-3, whereas (E, Z)-
diene 4 is obtained by the decarboxylation from complex 12. The selectivity between reductive elimination and decarboxylation may depend on the stereochemistry of the in&mediate 11 or 12. However, stetwchemical requhements far these mactions am not obvious.
cis-3
R,/B/LRz
w(o)_
lZE)4
1 IE.E)
scheme4 Since the intramolecular participation of the oxide anion to CO coot&a&
to the palladium (11 or 12 in
Scheme 4) is impossible in the reaction of cyclii alkenyloxirane 6, neither Blactone nor diene was famed in this case. When alkenyloxirane IIhaving electron-withdrawing substituent Ra such as akoxycarbonyl group wem subjectcd to the reaction with CO, no car6onylatkm product was formed and allylic alcohol and diene were produced as reduction products of the oxirane (Scheme 5). The ratio of the allylic alcohol Sf to the diene 41 increased on decrease of the Co pressme employed. Indeed, aRylic alcoho1.W was obtained selectively at atmospheric a0 pressure. The presence of CO, however, is essential for reduction of If to 41 and Sf. When the reactionoflfwarcarriedoutintheabsenceof(?O,noreactian~andlfwas~~
2138
fI$$pg&; tideiiaahydkk
tB(30 run); MeOH r. t.
4f
7%
sf
67%
Schem 5 Although the role of CO and the precise mechanisms for the reduction am not known, involvement of an alkoxycarbonyl complex and its reaction with alcohol to give n-allylpalladium
hydride complex am probable.
Indeed, formation of dlethyl carbonate and dlethyl oxalate in the reaction of lg was continned by GC-mass specuoscopy (Scheme 6).
(EtO)&O + (CODBth
BtOH Scheme 6
This research was supported by the Grant-in-Aid from the Ministry of Education, Science and Culture (No 03233238 and No 04217235) and the Asahi Glass Foundation.
REFERENCES (a) J. Tsuji, K. Sate, .and H. Okumoto, J. Org. Chem., 49, 1341 (1984). (b) J. Kiji. T. Okano, W. 1. Nishiumi, and H. Konishi, Chem. La., 1988, 957. (c) S-I. Murahashi, Y. Imada, Y. TanQuchi, and S. H$shiura, Terruhedko~ Lerr., 29,494s (1988). (d) D. Neibecker, J. Poirler, and I. Tkatchenko, J. Org. Chem., 54.2459 (1989). 2. M. Suzuki, Y. Oda, and R. Noyori, J. Am. Chem. Sot., 101,1424(1979). B. M. Trost and G. A. Molar&r, 1. Am. Chem. Sot., 103,5969 (1981); J. Tsuji, H. Kataoka, and Y. 3. Kobaylishi, Terrahedren’E.ett., 22.2575 (1981). 4. M. Oshima, H. Yamaxakl, I. Shimizu, M. Nisar, and J. Tsuji. J. Am. Chem. Sot., 111.6280 (1989).
(Received in Japan 24 December 1992)