Highly efficient chemical fixations of carbon dioxide and carbon disulfide by cycloaddition to aziridine under atmospheric pressure

Article abstract of DOI:10.1016/j.tetlet.2003.09.011

Cycloaddition of aziridine with carbon dioxide was successfully catalyzed by alkali metal halide or tetraalkylammonium halide to give the corresponding 5-membered cyclic urethane, 1,3-oxazolidin-2-one, selectively. The reaction can be performed at ambient

Full text of DOI:10.1016/j.tetlet.2003.09.011

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 44 (2003) 7889–7891
Highly efficient chemical fixations of carbon dioxide and carbon
disulfide by cycloaddition to aziridine under atmospheric pressure
a
b
b
c
d,
Atsushi Sudo, Yosuke Morioka, Eri Koizumi, Fumio Sanda and Takeshi Endo *
a
Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka 820-8555, Japan
b
Chemical Resources Laboratory, Tokyo Institute of Technology, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8503, Japan
c
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Yoshida-honmachi, Sakyo-ku,
Kyoto 606-8501, Japan
d
Department of Polymer Science and Engineering, Faculty of Engineering, Yamagata University, Jonan, Yonezawa,
Yamagata 992-8510, Japan
Received 7 August 2003; revised 28 August 2003; accepted 3 September 2003
Abstract—Cycloaddition of aziridine with carbon dioxide was successfully catalyzed by alkali metal halide or tetraalkylammonium
halide to give the corresponding 5-membered cyclic urethane, 1,3-oxazolidin-2-one, selectively. The reaction can be performed at
ambient temperature under atmospheric pressure. Analoguous reaction of aziridine with carbon disulfide also successfully gave the
corresponding 5-membered cyclic dithiourethane, 1,3-thioxazolidine-2-thione.
©
2003 Published by Elsevier Ltd.
Development of highly efficient methods for chemical
as a catalyst, and contamination by the corresponding
polyurethane.
fixation of CO and its efficient utilization as a C1
2
building block is one of the most urgent subjects to
solve the recent problems of earth pollution and deple-
tion of fossil fuels. In order to minimize the energy
consumption for utilization of CO2 as a chemical
resource, the ideal systems will be operated at ambient
temperature under atmospheric pressure. Among the
In this paper, we report the first selective synthesis of
2-oxazolidinone by cycloaddition of CO with aziridine
2
at ambient temperature under atmospheric pressure. As
the catalysts, alkali metal halides or tetraalkyl ammo-
nium salts were employed, which have been found to be
1
–4
various approaches studied so far,
the reaction of
highly effective catalysts for cycloaddition of atmo-
5
–10
10
CO with epoxide has emerged as an efficient one.
spheric CO
2
with epoxide by our previous studies.
A
2
similar cycloaddition of CS , which is a sulfur analogue
2
Aziridine, a nitrogen analogue of epoxide, has also high
ring strain, and is a hopeful candidate as a highly
reactive compound that can react with relatively inert
of CO , is also reported herein.
2
The reaction of commercially available 2-methyl-
aziridine (MeAz) with CO was performed in the pres-
ence of alkali metal halide as a catalyst (Scheme 1).
CO was supplied to the reaction vessel from the
CO without its intensive activation. On the analogy
2
2
from the cycloaddition reaction of CO with epoxides
2
that gives cyclic carbonates, the reaction of aziridine
2
with CO would lead to formation of the corresponding
equipped balloon without pressuring. At first, lithium
bromide, which is one of the most effective catalysts for
2
5
-membered cyclic urethane, 1,3-oxazolidin-2-one. Sev-
11–15
eral reports on this reaction have been reported,
the cycloaddition of CO with epoxide, was employed
2
however, they suffer from requirements of high pres-
sure, high temperature, employment of toxic compound
as a catalyst (Table 1, run 3). After the reaction for 24
h, we found that 4-methyl-1,3-oxazolidin-2-one (1a)
Keywords: aziridine; cycloaddition; carbon dioxide; atmospheric pres-
sure; carbon disulfide.
*
Corresponding author. Tel./fax: +81-238-26-3092; e-mail: tendo@
yz.yamagata-u.ac.jp
Scheme 1.
0
040-4039/$ - see front matter © 2003 Published by Elsevier Ltd.
doi:10.1016/j.tetlet.2003.09.011

7
890
A. Sudo et al. / Tetrahedron Letters 44 (2003) 7889–7891
Table 2. Cycloaddition of CO with 2-methylaziridine
Table 1. Cycloaddition of CO with 2-methylaziridine
2
2
+
−
a
(MeAz) catalyzed by tetrabutylammonium halide (n-
(
MeAz) catalyzed by alkali metal halide (M X ) in THF
+
− a
Bu N X )
4
Run
Catalyst
Yield (%)b
Run
X
Solvent
Temperature
Yield (%)b
1
2
3
4
5
None
LiCl
LiBr
LiI
NaBr
NaBr
KBr
0
1
2
3
4
5
6
7
Cl
Br
Br
Br
Br
Br
I
THF
THF
rt
rt
rt
rt
0°C
40 C
rt
22
95
72
10
52
67
63
Trace
74
32
37
76
CH CN
3
MeOH
THF
THF
c
6
o
c
7
62
THF
a
+
−
Conditions: [MeAz] =0.875 M, [MeAz] /[M X ]=5.0, at room
0
0
a
+
−
Conditions: [MeAz] =0.875 M, [MeAz] /[n-Bu N X ]=20, for 24
h.
Isolated by bulb-to-bulb distillation.
temperature, for 24 h.
Isolated by bulb-to-bulb distillation.
The reaction was carried out in the presence of 5 mol% 18-crown-6.
0
0
4
b
c
b
was given as a sole product. The corresponding
regioisomer, 5-methyl-1,3-oxazolidin-2-one, was not
1
detected at all by GC or by 300 MHz H NMR analysis
of the crude mixture. Thus, bulb-to-bulb distillation of
the mixture gave pure 1a in 74% yield. Other alkali
metal halides also catalyzed the reaction. A series of
reactions using lithium salts showed the superiority of
bromide as a counter anion (runs 2–4). Sodium bro-
mide and potassium bromide were also effective cata-
lysts when they were solvated in THF by addition of
Scheme 2.
1
8-crown-6. It is noteworthy that the reaction smoothly
proceeds at room temperature under atmospheric pres-
sure, while the analogous reaction of epoxide requires
elevation of temperature to 100°C to achieve sufficient
1
0
reaction rate.
Scheme 3.
Quaternary ammonium salt was also an effective cata-
lyst for the reaction (Table 2). Tetrabutylammonium
bromide (TBAB) most efficiently catalyzed the reaction
to obtain 1a in excellent yield (run 2). The catalyst
efficiency largely depended on the counter anion (runs
There have been a few examples of the reaction of CS2
with aziridine to obtain the corresponding 5-membered
cyclic dithiourethane, 1,3-thioxazolidine-2-thione, how-
ever these suffer from requirement of using excess
amount of CS and of high operation tempera-
2
14,19–21
1, 2 and 7), and its order was Br>I>Cl, which is same
ture.
Since the product is hopeful as a precursor
as found in the aforementioned lithium halide-catalyzed
reaction. In addition, as can be seen from the results of
runs 2–6, THF and room temperature were the best
choice for the optimum conditions.
for bioactive compounds and chiral auxiliaries, devel-
opment of highly efficient catalytic system still remains
a significant challenge.
Table 3 shows the conditions employed for the equimo-
2
-Phenylaziridine (PhAz) also can be used as a sub-
lar reaction of CS with MeAZ and the corresponding
2
strate for the present reaction system (Scheme 2). In
this case, the reaction did not proceed at room temper-
ature. Thus we used N-methylpyrrolidone (NMP) as a
less volatile solvent and carried out the reaction at
results. All alkali metal halides used and TBAB cata-
Table 3. Cycloaddition of CS with 2-methylaziridine
2
a
(
MeAz) in THF
1
00°C. Under the conditions, lithium bromide
Run
Catalyst
Yield (%)b
efficiently catalyzed the reaction to give 4-phenyloxazo-
lidin-2-one (1b) in 70% yield as a sole product.
1
2
3
4
5
6
7
8
None
LiCl
LiBr
LiI
NaBr
NaI
0
76
92
65
91
73
82
94
Encouraged by the successful results of CO -fixation
using the aziridines as a substrate, we next targeted an
2
analogous CS -fixation (Scheme 3). CS is a sulfur
2
2
analogue of CO , and is also an attractive C building
2
1
block to synthesize sulfur-containing functional
molecules. We have already reported the cycloaddition
KBr
TBAB
16
of CS with epoxide catalyzed by alkali metal halide.
2
a
The corresponding product is 5-membered cyclic dithio-
carbonate, which can be applied as a versatile monomer
Conditions: [MeAz] =0.875 M, [MeAz] /[catalyst]=20, at room
temperature, for 24 h.
0
0
17,18
b
to syntheses of various sulfur-containing polymers.
Determined by GC.

A. Sudo et al. / Tetrahedron Letters 44 (2003) 7889–7891
7891
lyzed the reaction at room temperature to give the
corresponding 5-membered cyclic dithiourethane, 4-
methyl-1,3-thiazolidine-2-thione (2). No regioisomer
4. Saito, S.; Nakagawa, S.; Koizumi, T.; Hirayama, K.;
Yamamoto, Y. J. Org. Chem. 1999, 64, 3975–3978.
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1
was detected by GC or by 300 MHz H NMR analysis
of the crude mixture. Similarly to the CO -fixation,
bromide was found to be a suitable anionic component
of catalysts for the present reaction. The reaction was
6. Darensbourg, D. J.; Lewis, S. J.; Rodgers, J. L.;
Yarbrough, J. C. Inorg. Chem. 2003, 42, 581–589.
2
7
8
9
. Calo, V.; Nacci, A.; Monopoli, A.; Fanizzi, A. Org. Lett.
2002, 4, 2561–2563.
. Paddock, R. M.; Nguyen, S. B. T. J. Am. Chem. Soc.
found to be much faster than the CO -fixation. Actu-
2
ally, it does not take 24 h for complete conversion of
MeAz at room temperature when lithium bromide was
used as a catalyst: We found that it was completely
converted to 2 by GC analysis of the reaction mixture
at 30 min. Furthermore, the reaction proceeded
smoothly even at −40°C to give 2 quantitatively within
2
001, 123, 11498–11499.
. Nozaki, K.; Nakano, K.; Hiyama, T. J. Am. Chem. Soc.
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1
1
1
1
1
6
30 min. Further study on kinetics of the reaction is
needed.
2
In summary, cycloadditions of CO and its sulfur ana-
2
4
logue, CS2, with aziridine were found to be hopeful
candidates as methods for their chemical fixation. The
fixations can be operated under atmospheric pressure at
room temperature by employing alkali metal halide or
quaternary ammonium salt as a catalyst, which are
stable and easily handled. The present systems will be
further improved to be ideally environmentally friendly
ones by more detailed studies on reaction mechanism
and further optimization of the conditions. Similar
reactions of aziridines having various substituents are
under investigation to clarify the scope and limitation
of the present system.
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