Silver-catalyzed efficient synthesis of vinylene carbonate derivatives from carbon dioxide

Article abstract of DOI:10.1055/s-0033-1341047

It was found that the silver salt and base was an efficient catalytic system for the reaction of the secondary propargylic alcohol with carbon dioxide to afford various corresponding vinylene carbonate derivatives in good to high yields under mild conditions. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0033-1341047

1178▌
LETTER
lSetitelrver-Catalyzed Efficient Synthesis of Vinylene Carbonate Derivatives from
Carbon Dioxide
Vinylene Carbonate Derivatives
Rie Ugajin, Satoshi Kikuchi, Tohru Yamada*
Department of Chemistry, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, 223-8522, Japan
Fax +81(45)5661716; E-mail: yamada@chem.keio.ac.jp
Received: 23.01.2014; Accepted after revision: 28.02.2014
O
O
O
O
DBU (100 mol%)
silver salt (10 mol%)
Abstract: It was found that the silver salt and base was an efficient
catalytic system for the reaction of the secondary propargylic alco-
hol with carbon dioxide to afford various corresponding vinylene
carbonate derivatives in good to high yields under mild conditions.
OH
O
O
Ph
CO2 (1.5 MPa)
H
Ph
Ph
Key words: alkynes, vinylene carbonates, carbon dioxide, silver,
isomerization, Lewis acids
A
B
Scheme 1 Formation of vinylene carbonate
Carbon dioxide is usually generated as a waste in the hu-
man living process. Much effort has been expended for
the development of the effective utilization of carbon di-
oxide in organic syntheses. However, carbon dioxide is
thermodynamically stable and has a low reactivity due to
the highly oxidized state of the carbon atom. Therefore,
high temperature and high pressure are required to obtain
satisfactory results.
known to be a highly toxic reagent, thus a safer method
was required. Although some improved methods in which
bis(trichloromethyl)carbonate7 or carbodiidmidazole8
was used as the alternative reagent of phosgene were de-
veloped, the number of substrates was still limited. The
dehydrogenchlorination from chloroethylene carbonate
was also reported to afford the corresponding vinylene
carbonate derivatives.9 However, in order to obtain the
starting material, it required the radical chlorination of cy-
clic carbonate with chlorine and ultraviolet light. It was
also reported that the aryl-substituted vinylene carbonate
was formed by the coupling reaction of vinylene carbon-
ate with aryl bromide,10 however, much waste was gener-
ated as a salt. Therefore, the reaction illustrated in Scheme
1 would be an attractive and ideal method for the synthesis
of vinylene carbonate derivatives without any waste and
using the much safer carbon dioxide instead of phosgene.
We now report the efficient synthesis of aryl-substituted
vinylene carbonate catalyzed by a silver salt from carbon
dioxide.
We recently reported that a silver catalyst could efficient-
ly mediate the carbon dioxide incorporation into various
alkynyl derivatives to afford the corresponding cyclic car-
bonate, oxazolidinone, lactone, and benzoxazin-2-one de-
rivatives with the Z-olefin under mild reaction
conditions.1 In these reactions, the efficient activation of
the C–C triple bond by silver salts would be the key step
for producing the corresponding products in high yields,
which was supported by DFT calculations of the model
substrate with a model base.2 It was reported that the reac-
tion of tertiary propargylic alcohols and carbon dioxide
was catalyzed by silver acetate with DBU to afford the
corresponding cyclic carbonate in high to excellent
yields.1a When we applied this catalytic system to the re-
action of a secondary propargylic alcohol, the predicted
cyclic carbonate was not obtained although another new
spot was detected by TLC analysis. After some additional
analyses of this compound including NMR, FTIR, and
GC–MS, it was found that the vinylene carbonate deriva-
tive A was produced (Scheme 1).
The reaction of propargylic alcohol 1a with carbon diox-
ide was carried out with silver acetate and one equivalent
of DBU under the same previously reported conditions.
However, the yield was not satisfactory (58% yield) and
the starting alcohol 1a remained with the low material bal-
ance. Although an excess of DBU was employed for this
reaction in order to improve the yield, the yield had de-
creased to 29% contrary to our expectation. These results
initially urged us to investigate the quantity of DBU (Ta-
ble 1). When the amount of DBU was gradually decreased
from 100 mol% to 40 mol%, the yield was increased and
it was found that the corresponding product 2a was ob-
tained in 94% yield in the presence of 40 mol% DBU (Ta-
ble 1, entries 2–6).11–13 However, the yield of the
corresponding vinylene carbonate 2a had decreased to
70% when 30 mol% DBU was used, and the correspond-
ing cyclic carbonate 3a was formed in 18% yield (Table
1, entry 7). The yield of 2a drastically decreased in the
presence of 20 mol% DBU although the cyclic carbonate
Vinylene carbonate derivatives are useful as the prodrug
for drug-delivery systems3 and are used as an electrolyte
additive of lithium ion batteries,4,5 however, there are few
synthetic methods of the vinylene carbonate derivatives. It
was reported that the vinylene carbonate derivative was
produced by the reaction of an α-hydroxy ketone and its
synthetic equivalent with phosgene,6 but phosgene is
SYNLETT 2014, 25, 1178–1180
Advanced online publication: 27.03.2014
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6
DOI: 10.1055/s-0033-1341047; Art ID: ST-2014-U0066-L
© Georg Thieme Verlag Stuttgart · New York

LETTER
Vinylene Carbonate Derivatives
1179
3a was obtained in 23% yield (Table 1, entry 8). No prod- the reaction of 1-phenylprop-2-yn-1-ol (1k) to produce
ucts (2a and 3a) were observed when the amount of DBU the corresponding product 2k in 70% yield. When sil-
decreased to 10 mol% (Table 1, entry 9).
ver(II) picolinate was used as the silver salt instead of sil-
ver acetate, the reaction of the substrate having the
cinnamyl moiety proceeded to afford the corresponding
vinylene carbonate 2l in good yield although a longer re-
action time was required.
Table 1 Examination of DBU Quantitya
CO2 (1.5 MPa)
DBU (X mol%)
AgOAc (10 mol%)
OH
Ph
toluene, 30 °C
24 h
H
CO2 (1.5 MPa)
O
n-Bu
DBU (40 mol%
OH
R2
1a
O
AgOAc (10 mol%)
O
O
O
R1
O
O
O
H
toluene, 30 °C
R1
+
O
n-Bu
n-Bu
Ph
1
2
Ph
Ph
O
O
O
O
O
2a
3a
O
O
O
O
n-Bu
n-Bu
Entry
DBU (mol%) Yield of 2a (%)b Yield of 3a (%)b
n-Bu
1
2
3
4
5
6
7
8
9
150
100
80
29
–
58
–
Br
60
–
2b: 89%
(24 h)
2c: 88%
(39 h)
2a: 94%
(24 h)
60
83
–
O
50
86
–
O
O
O
O
O
O
n-Bu
40
94
–
O
O
30
70
18
23
trace
Ph
Ph
Ph
20
39
10
trace
2e: 87%
(47 h)
2f: 86%
(27 h)
2d: 82%
(42 h)
a The reaction was performed on a 0.3 mmol scale.
b Isolated yields.
O
O
O
O
O
O
O
O
O
The reactions of several secondary alcohols with carbon
dioxide were carried out in the presence of 10 mol% silver
acetate with 40 mol% DBU (Scheme 2). The substrates
derived from hex-1-yne were initially subjected to these
reaction conditions. The reaction of secondary propargyl-
ic alcohols having a 4-tolyl group (1b), 4-bromophenyl
group (1c), and 2-naphthyl group (1d) were smoothly per-
formed using this reaction system to afford the corre-
sponding vinylene carbonate derivatives 2a–d in high
yields. Next, the reactions of various alkyl-substituted al-
kyne derivatives were carried out. The substrates 1e and
1f having a linear aliphatic alkyne, such as pent-1-yne and
5-phenylpent-1-yne, were transformed into the corre-
sponding products 2e and 2f in high yields, respectively.
This catalytic system was also applied to the reaction of
branched aliphatic alkyne derivatives, such as 3-methyl-
hex-1-yne and 3,3-dimethylbut-1-yne derivatives 1g and
1h, to produce the corresponding vinylene carbonate de-
rivatives 2g and 2h in excellent yields. It was found that
the ether group and siloxy group used under the stated re-
action conditions and the corresponding vinylene carbon-
ate derivatives 2i and 2j were obtained in good yields,
respectively. This catalytic system was also employed for
MeO
Ph
Ph
Ph
2h: 97%
(96 h)
2i: 67%
(24 h)
2g: 99%
(72 h)
O
O
O
O
O
O
O
O
O
TBSO
Ph
Ph
Ph
2l: 62%
2k: 70%
(24 h)
2j: 65%
(48 h)
(216 h)
Scheme 2 The reaction of secondary propargylic alcohols (see the
Supporting Information for reaction conditions). Isolated yield is de-
scribed. a For compound 2l: silver(II) picolinate was used instead of
silver acetate.
A plausible reaction mechanism was assumed to be as fol-
lows (Scheme 3): the cyclic carbonate would be first
formed and then isomerization of the olefin would occur
to afford the more thermodynamic stable vinylene carbon-
ate derivatives.14
© Georg Thieme Verlag Stuttgart · New York
Synlett 2014, 25, 1178–1180

1180
R. Ugajin et al.
LETTER
(f) Sakamoto, F.; Ikeda, S.; Tsukamoto, G. Chem. Pharm.
Bull. 1984, 32, 2241.
O
O
O
O
OH
R2
CO2
O
O
(4) Satoa, K.; Zhaob, L.; Okadab, S.; Yamaki, J. J. Power
Sources 2011, 196, 5617; and references cited therein.
(5) There are some patents, for example: (a) Simon, B.; Boeuve,
J.-P. US 005626981A, 1997. (b) Barker, J.; Gao, F. US
005712059A, 1998. (c) Naruse, Y.; Fujita, S.; Omaru, A. US
005714281A, 1998.
R1
R1
Ag+
DBU
H
R1
R2
R2
Scheme 3 Plausible reaction mechanism of the formation of vinyl-
ene carbonate
(6) (a) Schobert, R. Angew. Chem., Int. Ed. Engl. 1988, 27, 855.
(b) Gauthier, J. Y.; Leblanc, Y.; Black, W. C.; Chan, C.-C.;
Cromlish, W. A.; Gordon, R.; Kennedey, B. P.; Lau, C. K.;
Léger, S.; Wang, Z.; Ethier, D.; Guay, J.; Mancini, J.;
Riendeau, D.; Tagari, P.; Vickers, P.; Wong, E.; Xu, L.;
Prasit, P. Bioorg. Med. Chem. Lett. 1996, 6, 87. (c) Sun, C.-
Q.; Cheng, P. T. W.; Stevenson, J.; Dejneka, T.; Brown, B.;
Wang, T. C.; Robl, J. A.; Poss, M. A. Tetrahedron Lett.
2002, 43, 1161. (d) Dürr, S.; Höhlein, U.; Schobert, R.
J. Organomet. Chem. 1993, 458, 89.
In summary, it was found that the silver salt/DBU system
was applied to the reaction of secondary propargylic alco-
hols including internal and terminal alkyne derivatives
with carbon dioxide and various corresponding vinylene
carbonates were produced in good to high yields. Based
on this catalytic system, the substrate having the cinnamyl
moiety was found to be transformed into the correspond-
ing vinylene carbonate in good yield when silver(II) pico-
linate was used as the silver salt. Further investigations are
currently under way.
(7) Sahu, D. P. Indian J. Chem., Sect. B: Org. Chem. Incl. Med.
Chem. 2002, 41, 1722.
(8) Papageorgiou, G.; Corrie, J. E.T. Tetrahedron 1997, 53,
3917.
(9) (a) Fischler, H.-M.; Heine, H.-G.; Hartmann, W.
Tetrahedron Lett. 1972, 13, 1701. (b) Newman, M. S.;
Addor, R. W. J. Am. Chem. Soc. 1953, 75, 1263.
(10) Kim, K. H.; Park, B. R.; Lim, J. W.; Kim, J. N. Tetrahedron
Lett. 2011, 52, 3463.
(11) When the reaction was carried out under the balloon
pressure, the yield was decreased into 77% yield.
(12) General Procedure
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett.SnoIufproig
m
iotSrat
ungIifoop
r
t
References and Notes
(1) (a) Yamada, W.; Sugawara, Y.; Cheng, H.-M.; Ikeno, T.;
Yamada, T. Eur. J. Org. Chem. 2007, 2604. (b) Yoshida, S.;
Fukui, K.; Kikuchi, K.; Yamada, T. J. Am. Chem. Soc. 2010,
132, 4072. (c) Yoshida, S.; Fukui, K.; Kikuchi, S.; Yamada,
T. Chem. Lett. 2009, 38, 786. (d) Kikuchi, S.; Sekine, K.;
Ishida, T.; Yamada, T. Angew. Chem. Int. Ed. 2012, 51,
6989. (e) Ishida, T.; Kikuchi, S.; Tsubo, T.; Yamada, T. Org.
Lett. 2013, 15, 848. (f) Ishida, T.; Kikuchi, S.; Yamada, T.
Org. Lett. 2013, 15, 3710.
The reaction was performed using a pressure test tube
equipped with a stirring bar in a 50 mL autoclave. To a
solution of propargyl alcohol 1 (0.30 mmol) and AgOAc
(0.030 mmol, 5.0 mg) in toluene (2.0 mL) was added DBU
(0.12 mmol, 18 μL) under an inert gas. Immediately, CO2
gas was purged, and the reaction mixture was stirred at 30 °C
under 1.5 MPa CO2 pressure. After the reaction was
completed, the purification by column chromatography
[SiO2, eluted with n-hexane–EtOAc (100:1)] gave the
corresponding carbonate 2.
(2) Kikuchi, S.; Yoshida, S.; Sugawara, Y.; Yamada, W.;
Cheng, H.-M.; Fukui, K.; Sekine, K.; Iwakura, I.; Ikeno, T.;
Yamada, T. Bull. Chem. Soc. Jpn. 2011, 84, 698.
(3) (a) Carini, D. J.; Ardecky, R. J.; Ensinger, C. L.; Pruitt, R.
R.; Wexler, P. C.; Wong, S.-M.; Huang, B. J.; Aungst, J. R.;
Timmermans, P. B. M. W. M. Bioorg. Med. Chem. 1994, 4,
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M.; Sotomura, M.; Tsukamoto, G. Chem. Pharm. Bull. 1991,
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D. S.; Glass, J. D.; Holahan, M. A.; Renyer, M. L.; Rork, G.
S.; Sitko, G. R.; Stranieri, M. T.; Stupienski, R. F.;
(13) Representative Experimental Data
4-Pentyl-5-phenyl-1,3-dioxol-2-one (2a)
Reaction time 24 h; yield 96%; 66.9 mg; colorless oil. 1H
NMR (400 MHz, CDCl3): δ = 0.91 (t, J = 7.1 Hz, 3 H), 1.37
(m, 4 H), 1.71 (m, 2 H), 2.69 (t, J = 7.6 Hz, 2 H), 7.37–7.48
(m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 13.9, 22.3, 24.8,
26.5, 31.1, 125.2, 125.6, 128.9, 129.0, 137.2, 139.2, 152.4.
IR (KBr): 2958, 2932, 2862, 1821, 1449, 1248, 1188, 1098,
1057, 1026, 977, 760, 692. ESI-HRMS: m/z calcd for
C14H17O3+ [M + H]+: 233.1172; found: 233.1177.
(14) See the Supporting Information; similar isomerizations have
been observed by some groups, see: (a) Hashmi, A. S. K.;
Rudolph, M.; Schymura, S.; Visus, J.; Frey, W. Eur. J. Org.
Chem. 2006, 4905. (b) Wong, V. H. L.; Andy Hor, T. S.; Hii,
K. K. Chem. Commun. 2013, 49, 9272.
Veerapanane, H.; Cook, J. J. J. Med. Chem. 1996, 39, 480.
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Lafontaine, Y.; Delorme, D.; Ferreira, S. S.; Viens, F.;
Arhin, F. F.; Sarmiento, I.; Lehoux, D.; Fadhil, I.; Laquerre,
K.; Liu, J.; Ostiguy, V.; Poirier, H.; Moeck, G.; Parr, T. R.
Jr.; Rafai Far, A. J. Med. Chem. 2008, 51, 6955.
Synlett 2014, 25, 1178–1180
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