A facile method for the synthesis of 1,3-oxathiolan-2-ones by reaction of oxiranes, sulfur, and carbon monoxide

Article abstract of DOI:10.1016/j.tet.2006.03.081

A new method for the synthesis of 1,3-oxathiolan-2-ones has been developed. When oxiranes were allowed to react with sulfur in the presence of a catalytic amount of sodium hydride under pressurized carbon monoxide, the three-component coupling of oxiranes

Full text of DOI:10.1016/j.tet.2006.03.081

Tetrahedron 62 (2006) 5803–5807
A facile method for the synthesis of 1,3-oxathiolan-2-ones
by reaction of oxiranes, sulfur, and carbon monoxide
*
Yutaka Nishiyama, Chisato Katahira and Noboru Sonoda
*
Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-8680, Japan
Received 21 November 2005; accepted 14 March 2006
Available online 2 May 2006
Abstract—A new method for the synthesis of 1,3-oxathiolan-2-ones has been developed. When oxiranes were allowed to react with sulfur in
the presence of a catalytic amount of sodium hydride under pressurized carbon monoxide, the three-component coupling of oxiranes, sulfur,
and carbon monoxide smoothly proceeded to give the 1,3-oxathiolan-2-ones in moderate to good yields. The reaction proceeded with a high
regioselectivity and stereospecificity. For the reaction of oxiranes possessing an aromatic ring, the yields of the 1,3-oxathiolan-2-ones were
lower than that of the oxiranes possessing no aromatic ring due to the formation of alkenes and thiiranes as byproducts. However, the product
yields were improved by the addition of a catalytic amount of selenium.
Ó 2006 Elsevier Ltd. All rights reserved.
1. Introduction
of 1,3-oxathiolan-2-one sometimes occurred under these re-
action conditions, and thiirane was formed as a byproduct.7
The development of the process to replace the use of phos-
gene as a carbonylating reagent has received considerable
attention in recent years due to environmental and industrial
concerns. Carbon monoxide is one of the promising agents
to replace phosgene; the development of new methods for
the carbonylation of various organic compounds with carbon
monoxide could have a significant impact on organic and
industrial chemistries.1
We have now developed a facile method for the synthesis of
1,3-oxathiolan-2-ones by the reaction of oxiranes with sulfur
and carbon monoxide in the presence of a catalytic amount
of sodium hydride under mild reaction conditions.8,9
Furthermore, it was confirmed that the yields of the 1,3-
oxathiolan-2-ones possessing an aromatic ring were
improved by the addition of a selenium catalyst.
Since 1,3-oxathiolan-2-one is an important synthetic inter-
mediate in organic2 and polymer sciences,3 considerable
attention has been devoted to the development of a conve-
nient method for the synthesis of 1,3-oxathiolan-2-one.
Although various synthetic methods of 1,3-oxathiolan-2-
one, such as the carbonylation of b-hydroxy thiol with phos-
gene, the treatment of oxirane with carbonyl sulfide in the
presence of triethylamine, the base-catalyzed cyclization
of the imidazolide derivative prepared by the treatment of
epoxy alcohol with thiocarbonyl diimidazole, the oxidation
of 2-alkoxy-1,3-oxathiolane, and the acid-assisted cycliza-
tion of 2-hydroxyethyl thiocarbonate have been reported,2–6
these methods have the following disadvantages: (i) the use
of poisonous phosgene and carbonyl sulfide, (ii) the use of
intolerable and odorous thiol, (iii) the harsh reaction condi-
tions for the preparation of carbonyl sulfide, and (iv) limita-
tion of starting materials. Furthermore, the decarboxylation
2. Results and discussion
In order to determine the optimized reaction conditions,
2-decyloxirane (1a) was allowed to react with sulfur and
carbon monoxide under various reaction conditions and
the results are shown in Table 1. When 1a was treated with
sulfur (5 equiv) in the presence of sodium hydride under
pressurized carbon monoxide (10 kg cmꢀ2) in THF solvent
at 60 ꢁC for 3 h, 5-decyl-1,3-oxothiolan-2-one (2a) was
obtained in 96% yield (entry 5). The yield of 2a decreased
when the reaction was carried out at lower reaction
temperatures and carbon monoxide pressures (entries 5
and 13–16). The product yield was also affected by the
amount of sulfur used (entries 1–5). Although 1a was cou-
pled with sulfur and carbon monoxide, even using 1,4-
dioxane, DMSO, DMF, and acetonitrile instead of THF as
the solvent, the best yield was observed in the THF solvent
(entries 5 and 7–10). In the case of hydrocarbon solvents,
such as toluene and hexane, the reaction did not proceed
* Corresponding authors. Tel.: +81 6 6368 1121; fax: +81 6 6339 4026;
e-mail: nishiya@ipcku.kansai-u.ac.jp
0040–4020/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.03.081

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Y. Nishiyama et al. / Tetrahedron 62 (2006) 5803–5807
Table 1. The reaction of 2-decyloxirane with carbon monoxide and sulfur
Table 3. The reaction of various oxiranes with carbon monoxide and sulfura
under various reaction conditionsa
R1
R2
R3
R3
cat.NaH
THF
C10H21
R2
R1
+
+
CO
S
NaH
O
S
C10H21
O
+
+
CO
S
O
S
O
solvent
O
O
Entry
R1
R2
R3
Yield (%)b
Entry
Sulfur
(mmol)
Solvent
Temp
(ꢁC)
CO
Yield
(%)b
(kg cmꢀ2
)
1
2
3
n-C10H21
C2H5
CH3
H
CH3
Ph
H
H
CH3
H
H
H
95
87
99
61
4
39
32
4
1
2
3
4
2
4
6
THF
THF
THF
THF
THF
THF
1,4-Dioxane
DMSO
DMF
Acetonitrile
Toluene
Hexane
THF
THF
THF
60
60
60
60
60
60
60
60
60
60
60
60
50
40
60
60
10
10
10
10
10
10
10
10
10
10
10
10
10
10
5
28
67
76
85
96 (92)
95
22
56
82
60
0
(CH2)4
4
5c
6
CH3
H
H
H
H
CH3
8
H
H
H
H
H
5
10
10
10
10
10
10
10
10
10
10
10
10
7
8
9
10
4-Tol
6c
7
4-BrC6H5
PhCH2
PhOCH2
53
24
8
9
H
Reaction conditions: oxirane (2 mmol), S (10 mmol), CO (10 kg cmꢀ2),
NaH (0.5 mmol), and THF (2 mL) at 60 ꢁC for 3 h.
GC yield.
a
10
11
12
13
14
15
16
b
c
0
The reaction was carried out at 150 ꢁC for 8 h.
72
29
37
0
sulfur and carbon monoxide in the presence of a catalytic
amount of sodium hydride, and these results are shown in
Table 3. The yields of the products were influenced by the
structure of the oxiranes. For the 2-alkyl and 2,2-dialkyl
substituted oxiranes, 5-alkyl and 5,5-dialkyl substituted
1,3-oxathiolane-2-ones were obtained in 95, 87, and 99%
yields, respectively, (entries 1–3). The treatment of 7-oxa-
bicyclo[4.1.0]heptane with sulfur and carbon monoxide
produced 4,5-tetramethylene-1,3-oxathiolan-2-one in a 61%
yield (entry 4). For the sterically hindered oxirane, such as
2,2,3-trimethyloxirane, the product yield was low (entry
5). For the reaction of the oxiranes possessing an aromatic
ring, such as 2-phenyl-, 2-(4-methylphenyl)-, 2-(4-bromo-
phenyl)-, 2-benzyl-, and 2-phenoxymethyl oxirane, the
yields of the 1,3-oxathiolan-2-ones were low compared to
those of the oxiranes possessing no aromatic ring due to
the formation of alkene, thiirane, and oligomers of oxirane
as byproducts (entries 6–10).
THF
1
a
Reaction conditions: 2-decyloxirane (2 mmol), NaH (2 mmol), and
solvent (2 mL) for 3 h.
GC yield. The number in parenthesis shows the isolated yield.
NaH (0.5 mmol) was used.
b
c
and 1a (92 and 95%, respectively) was recovered (entries 11
and 12). In this reaction, it is possible to still further reduce
the amount of sodium hydride (25 mol %) and form 2a in
95% yield (entry 6).
The reaction of 1a with sulfur and carbon monoxide was
next examined in the presence of various metal hydrides,
and these results are shown in Table 2.10 Although the other
metal hydrides, lithium, potassium, and calcium hydrides
and sodium borohydride also functioned as a base, the yields
of 2a were distinctly decreased (entries 2, 3, 5, and 6). For
the reaction in the presence of potassium hydride, it is inter-
esting to note that the yield of 2a was dramatically increased
by the addition of dibenzo-18-crown-6, which strongly binds
with the potassium cation (entry 4).
The reaction of cis-2,3-disubstituted oxiranes, such as cis-
2,3-dimethyl- and 2,3-diphenyloxiranes, stereospecifically
proceeded and formed the trans-4,5-disubstituted 1,3-oxa-
thiolan-2-ones in moderate yields (Scheme 1). Similarly,
trans-2,3-dimethyloxirane produced the cis-4,5-dimethyl-
1,3-oxothiolan-2-one, however, for trans-2,3-diphenyl-
oxirane, cis-4,5-diphenyl-1,3-oxathiolan-2-one was not
confirmed and the oxirane (86%) was recovered.
To determine the scope and limitation of the synthesis of the
1,3-oxathiolan-2-ones, various oxiranes were reacted with
Table 2. The reaction of 2-decyloxirane with carbon monoxide and sulfur in
the presence of metal hydridea
C10H21
R
H
metal hydride
C10H21
+
+
CO
S
O
S
O
cat.NaH (0.5 mmol)
H
R
THF
H
R
H
R
+
O
+
S
CO
O
S
THF (2 mL)
O
(2 mmol) (10 mmol) (10 kg cm-2
)
120 °C, 6 h
O
Entry
Metal hydride
Yield (%)b
61 %
35 %
R = Me
R = Ph
1
2
LiH
NaH
KH
KH
CaH2
NaBH4
0
95
28
82
61
7
R
H
R
3
cat.NaH (0.5 mmol)
THF (2 mL)
O
4c
5
H
H
R
R +
H
+
S
CO
O
S
6
O
(2 mmol) (10 mmol) (10 kg cm-2
)
120 °C, 6 h
a
16 %
0 %
R = Me
R = Ph
Reaction conditions: 2-decyloxirane (2 mmol), S (10 mmol), CO (10 kg
cmꢀ2), metal hydride (0.5 mmol), and THF (2 mL) at 60 ꢁC for 3 h.
GC yield.
b
c
Dibenzo-18-crown-6 (0.5 mmol) was added.
Scheme 1.

Y. Nishiyama et al. / Tetrahedron 62 (2006) 5803–5807
5805
Table 4. Selenium-catalyzed synthesis of 1,3-oxathiolan-2-onesa
Although the reaction pathway for the formation of 1,3-
R1
R2
R3
oxathiolan-2-one has not been fully clarified, one of the
plausible reaction pathways is shown in Scheme 2. It was
suggested that the preparation of carbonyl sulfide by the re-
action of sulfur and carbon monoxide was the first step in the
reaction. The hydride anion attacked the carbonyl sulfide to
give the corresponding thioformate anion (3).11 The attack
of 3 on the oxirane from the less hindered side then formed
an intermediate (4). Rotation of the carbon–carbon bond fol-
lowed by intramolecular cyclization gave the corresponding
1,3-oxathiolan-2-one and regenerated the hydride anion. For
the reaction of the trans-2,3-dimethyl or trans-2,3-diphenyl
substituted oxiranes, it was suggested that the rotation of the
carbon–carbon bond of 4 was strongly suppressed by the
steric effect and the oxygen anion attacked the b-carbon to
regenerate the oxirane.
R3
cat.Se, cat.NaH
R2
R1
+
+
CO
S
O
S
O
O
Entry
R1
Ph
R2
R3
Yield (%)b
1b
2
3
4
5
6
H
H
H
H
H
H
H
H
H
H
79
50
22
97
66
16
31
7
p-Tol
p-BrC6H5
PhCH2
PhOCH2
H
H
CH3
(CH2)4
7c
8c
9c,d
10e
CH3
H
Ph
CH3
CH3
CH3
Ph
H
CH3
10
4
CH3
a
Reaction conditions: epoxide (2 mmol), S (10 mmol), CO (10 atm), Se
(0.05 mmol), NaH (0.5 mmol), and THF (2 mL) at 60 ꢁC for 3 h.
GC yield.
b
c
d
e
R1
H
CO
The reaction was carried out at 120 ꢁC for 6 h.
cis-Stillbene (24%) was formed as byproduct.
The reaction was carried out at 150 ꢁC for 8 h.
H
R2
O
S
(NaH)n
SCO
S
(NaH)n
O
provides a useful method for the synthesis of the 1,3-oxa-
thiolan-2-ones.
R1
H
H
R2
S
CH
O
O
S
(NanHn-1
)
(NanHn-1
)
C
O
H
3. Experimental
(3)
3.1. General procedure
O
H
H
O
The 1H and 13C NMR spectra were recorded by 400 or 270
and 99.5 or 67.8 MHz spectrometers using CDCl3 as a sol-
vent with tetramethylsilane as an internal standard. IR spec-
tra were obtained using a FT-IR spectrophotometer. The mass
spectra were measured by GC–MS. Gas chromatography
(GC) was carried out using a spectrometer with flame-ioniz-
ing detector and a capillary column. 2-(4-Methylphenyl)
oxirane was synthesized by the oxidation of 4-methylstyrene
with MCPBA. Powdered sulfur, sodium hydride, and ele-
mental selenium were commercially available and used
without purification. The solvents oxiranes and amines
were distilled before use.
R1
R2
H
H
R1
R2
(NanHn-1
)
S
C
O
H
(4)
Scheme 2. A plausible reaction pathway.
We have recently reported that selenium acts as a catalyst for
the reaction of sulfur and carbon monoxide producing car-
bonyl sulfide in the presence of an amine.12 During the con-
tinuing study of the selenium-catalyzed reaction of sulfur
and carbon monoxide, it was found that various organosulfur
compounds having a thiolester (–C(]O)S–) group were
synthesized in moderate to good yields using this catalytic
reaction system under mild conditions.13 Based on these
results, we next investigated the application of the selenium-
catalyzed reaction system on the preparation of 1,3-oxathio-
lan-2-ones. Various oxiranes were allowed to react with
sulfur and carbon monoxide in the presence of a catalytic
amount of sodium hydride and selenium, and these results
are shown in Table 4. It is interesting to note that the
yields of the 1,3-oxathiolan-2-ones having an aromatic
ring were improved using the selenium-catalyzed reaction
system.14,15
3.2. General procedure for the synthesis of 1,3-oxathio-
lan-2-ones
In a 50 mL stainless steel autoclave were placed powdered
sulfur (10 mmol, 0.321 g), THF (2 mL), oxirane (2 mmol),
and NaH (0.5 mmol, 0.024 g in mineral oil). The apparatus
was flushed several times with carbon monoxide and then
charged with carbon monoxide at 10 kg cmꢀ2. The mixture
was heated with stirring at 60 ꢁC for 3 h. After the reaction
was complete, H2O was added to the resulting solution
and extracted with diisopropyl ether (15ꢂ3 mL). The com-
bined organic layer was dried over MgSO4. The organic
solvent was removed under reduced pressure. Purification by
column chromatography (hexane/AcOEt¼3/1) on silica gel
and HPLC (CHCl3) gave the corresponding 1,3-oxathiolan-
2-ones. The product was characterized by comparison of
its spectral data with those of authentic samples (5-decyl-
1,3-oxathiolan-2-one,16 5-ethyl-1,3-oxathiolan-2-one,17,18
In summary, we found that the reaction of oxiranes with
sulfur and carbon monoxide in the presence of a catalytic
amount of sodium hydride produced the corresponding
1,3-oxathiolan-2-ones. In addition, for the reaction of oxi-
ranes having an aromatic ring, the yields of the 1,3-oxathio-
lan-2-ones were improved by the addition of the selenium
catalyst. From the viewpoint of a simple operation, mild
reaction conditions, and good yields, the present reaction
4,5-tetramethylene-1,3-oxathiolan-2-one,19
methyl-1,3-oxathiolan-2-one,20 and 2-phenylthiirane21).
trans-4,5-di-

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Y. Nishiyama et al. / Tetrahedron 62 (2006) 5803–5807
3.3. General procedure for the selenium-catalyzed
synthesis of 1,3-oxathiolan-2-ones
39.795, 35.687; IR (neat) 2923, 1716, 764, 703 cmꢀ1; MS
194 (M+); yellow oil. Anal. Calcd for C10H10O2S: C,
61.83; H, 5.19; S, 16.51. Found: C, 62.04; H, 5.02; S, 16.53.
In a 50 mL stainless steel autoclave were placed powdered
sulfur (10 mmol, 0.321 g), elemental selenium (0.05 mmol,
0.004 g), THF (2 mL), oxirane (2 mmol), and NaH
(0.5 mmol, 0.024 g in mineral oil). The apparatus was flushed
several times with carbon monoxide and charged with carbon
monoxide at 10 kg cmꢀ2. The mixture was then heated with
stirring at 60 ꢁC for 3 h. After the reaction was complete,
H2O was added to the resulting solution and extracted with
diisopropyl ether (15ꢂ3 mL). The combined organic layer
was dried over MgSO4. The organic solvent was removed un-
der reduced pressure. Purification by column chromatography
(hexane/AcOEt¼3/1) on silica gel and HPLC (CHCl3) gave
the corresponding 1,3-oxathiolan-2-ones.
1
3.3.7. 5-(Phenoxymethyl)-1,3-oxathiolan-2-one. H NMR
(270 MHz, CDCl3) d 7.334–6.892 (m, 5H), 5.052–4.961
(m, 1H), 4.197 (d, J¼4.9 Hz, 2H), 3.641 (d, J¼7.3 Hz,
2H); 13C NMR (67.8 MHz, CDCl3) d 172.103, 157.548,
129.517, 121.643, 114.353, 77.749, 66.674, 33.130; IR
(neat) 1736, 1244, 1077, 755 cmꢀ1; MS 210 (M+); yellow
oil. Anal. Calcd for C10H10O3S: C, 57.13; H, 4.79; S,
15.25. Found: C, 57.32; H, 4.76; S, 15.21.
Acknowledgements
This research was supported by a Grant-in-Aid for Science
Research (No. 15550096) and Research and Development
Organization of Industry-University Cooperation from the
Ministry of Education, Culture, Sports, Science, and Tech-
nology of Japan.
3.3.1. 5,5-Dimethyl-1,3-oxathiolan-2-one. 1H NMR
(400 MHz, CDCl3) d 3.377 (s, 2H), 1.584 (s, 6H); 13C
NMR (100 MHz, CDCl3) d 171.663, 85.381, 42.426,
26.447; IR (neat) 2981, 2937, 1732 cmꢀ1; MS 132 (M+);
yellow oil. Anal. Calcd for C5H8O2S: C, 45.43; H, 6.10; S,
24.26. Found: C, 45.27; H, 6.21; S, 24.35.
3.3.2. 4,5,5-Trimethyl-1,3-oxathiolan-2-one. 1H NMR
(270 MHz, CDCl3) d 3.876 (q, J¼6.8 Hz, 1H), 1.552–
1.384 (m, 9H); 13C NMR (67.8 MHz, CDCl3) d 171.280,
88.165, 51.963, 25.997, 21.102, 16.075; IR (neat) 2996,
1730 cmꢀ1; MS 146 (M+); yellow oil. Anal. Calcd for
C6H10O2S: C, 49.29; H, 6.89; S, 21.93. Found: C, 49.51;
H, 6.72; S, 21.88.
References and notes
1. For recent reviews of carbonylation, see: (a) Dugal, M.; Koch,
D.; Naberfeld, G.; Six, C. In Applied Homogeneous Catalysis
with Organometallic Compounds, 2nd ed.; Wiley-VCH: 2002;
Vol. 3; (b) Handbook of Organopalladium Chemistry for
Organic Synthesis; Negishi, E., Ed.; Wiley: 2002; p 2691; (c)
Skoda-Foldes, R.; Kollar, L. Curr. Org. Chem. 2002, 6, 1097;
(d) Bates, R. W. In Comprehensive Organometallic Chemistry;
Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon:
Oxford, 1995; Vol. 12, p 349; (e) Colquhoun, H. M.; Thompson,
D. J.; Twigg, M. V. Carbonylation: Direct Synthesis of Carbonyl
Compounds; Plenum: New York, NY, 1991.
3.3.3. 5-Phenyl-1,3-oxathiolan-2-one. 1H NMR (400 MHz,
CDCl3) d 7.313–7.360 (m, 5H), 5.560 (dd, J¼6.8 and
9.4 Hz, 1H), 3.660 (dd, J¼6.8 and 10.8 Hz, 1H), 3.463
(dd, J¼9.4 and 10.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3) d 172.001, 136.206, 128.889, 128.559, 125.367,
81.686, 38.318; IR (neat) 1740, 770, 697 cmꢀ1; MS 180
(M+); yellow oil. Anal. Calcd for C9H8O2S: C, 59.98; H,
4.47; S, 17.79. Found: C, 60.21; H, 4.32; S, 17.67.
2. Roush, W. R.; Gustin, D. Tetrahedron Lett. 1994, 35, 4931.
3. Wang, P. C. Heterocycles 1986, 24, 329.
4. (a) Taganliev, A.; Rol’nik, L. Z.; Pastushenko, E. V.; Zlotskii,
S. S.; Rakhmankulov, D. L. Zh. Org. Khim. 1985, 21, 2206;
(b) Taganliev, A.; Rol’nik, L. Z.; Pastushenko, E. V.; Zlotskii,
S. S.; Rakhmankulov, D. L. Zh. Org. Khim. 1981, 17, 1539;
(c) Taganliev, A.; Rol’nik, L. Z.; Pastushenko, E. V.; Zlotskii,
S. S.; Rakhmankulov, D. L. Khim. Get. Soe. 1985, 919; (d)
Ethylene-Plastique S. A. BP 1, 1968, 135, 799; (e) Thiokol
Chemical Corp. USP 3, 1966, 240, 788; (f) Johnson, D. L.;
Fields, D. L. Chem. Abstr. 1963, 58, 12426; (g) Razuvaev,
G. A.; Etlis, V. S.; Grobov, L. N. Zh. Obshch. Khim. 1962,
32, 994; (h) Etlis, H. V. S.; Grobov, L. N.; Razuvaev, G. A.
Zh. Obshch. Khim. 1962, 32, 2940.
5. (a) Reynolds, D. D.; Massad, M. K.; Fields, D. L.; Johnson,
D. L. J. Org. Chem. 1961, 26, 5122; (b) Reynolds, D. D. U.S.
Patent 2,828,318, 1958; Chem. Abstr. 1958, 52, 14651; (c)
Reynolds, D. D. J. Am. Chem. Soc. 1957, 79, 4951.
6. Oku et al. recently reported the viable utilization of polycar-
bonate as a phosgene equivalent. In this paper, they have dis-
closed the reaction of polycarbonate with mercaptoethanol in
the presence of a catalytic amount of base giving 1,3-oxathio-
lan-2-one in good yields. See: Hata, S.; Goto, H.; Tanaka, S.;
Oku, A. J. Appl. Polym. Sci. 2003, 90, 2959.
3.3.4. 5-(4-Toly)-1,3-oxathiolan-2-one. 1H NMR (270 MHz,
CDCl3) d 7.244–7.139 (m, 4H), 5.516 (dd, J¼6.5 and
9.5 Hz, 1H), 3.628 (dd, J¼6.6 and 11.1 Hz, 1H) 3.450
(t, 1H), 2.307 (s, 3H); 13C NMR (67.8 MHz, CDCl3)
d 171.864, 138.658, 133.046, 129.040, 125.321, 81.747,
38.174, 20.822; IR (neat) 3030, 2923, 1738 cmꢀ1; MS 194
(M+); yellow oil. Anal. Calcd for C10H10O2S: C, 61.83;
H, 5.19; S, 16.51. Found: C, 61.71; H, 5.18; S, 16.28.
3.3.5. 5-(4-Bromophenyl)-1,3-oxathiolan-2-one. 1H NMR
(270 MHz, CDCl3) d 7.529–7.249 (m, 4H), 5.601 (dd,
J¼6.5 and 9.5 Hz, 1H), 3.761 (dd, J¼6.5 and 11.2 Hz,
1H), 3.507 (dd, J¼9.5 and 11.2 Hz, 1H); 13C NMR
(67.8 MHz, CDCl3) d 171.749, 135.276, 131.738, 127.123,
122.935, 80.925, 38.314; IR (KBr) 1719 cmꢀ1; MS 260
(M+); colorless crystals. Anal. Calcd for C9H7BrO2S: C,
41.72; H, 2.72; S, 12.37. Found: C, 41.85; H, 2.68; S, 12.35.
3.3.6. 5-Benzyl-1,3-oxathiolan-2-one. 1H NMR (400 MHz,
CDCl3) d 7.358–7.218 (m, 5H), 4.863 (quintet, J¼6.9 Hz,
1H), 3.416–2.990 (m, 4H); 13C NMR (100 MHz, CDCl3)
d 172.331, 134.771, 129.236, 128.765, 127.272, 81.257,
7. Barbero, M.; Degani, I.; Dughera, S.; Fochi, R.; Piscopo, L.
J. Chem. Soc., Perkin Trans. 1 1995, 189.

Y. Nishiyama et al. / Tetrahedron 62 (2006) 5803–5807
5807
8. We recently showed that the reaction of 2-alkyn-1-ols with
sulfur and carbon monoxide in the presence of triethylamine,
followed by copper (I)-catalyzed cyclization gave 4-alkyl-
idene-2-oxo-1,3-oxathiolanes in moderate to good yields.
See: Mizuno, T.; Nakamura, F.; Ishino, Y.; Nishiguchi, I.;
Hirashima, T.; Ogawa, A.; Kambe, N.; Sonoda, N. Synthesis
1989, 770.
9. Nishiyama, Y.; Katahira, C.; Sonoda, N. Tetrahedron Lett.
2004, 45, 8539.
10. The effect of various amines on this reaction was also investi-
gated, DBU; 56%, DBN; 23%, N-methylpyrrolidine; 0%,
triethylamine; 0%, pyridine; and 0%, NaOH.
I.; Sonoda, N. Tetrahedron 1994, 50, 5669; (d) Mizuno, T.;
Nishiguchi, I.; Hirashima, T.; Ogawa, A.; Kambe, N.; Sonoda,
N. Tetrahedron Lett. 1990, 30, 4773; (e) Mizuno, T.; Nishigu-
chi, I.; Hirashima, T.; Sonoda, N. Heteroat. Chem. 1990, 1, 157.
14. When the reaction solution was oxidized by air, a gray sele-
nium precipitate was recovered by filtration.
15. It was proposed that the concentration of carbonyl sulfide was
increased by the addition of the selenium catalyst. The yield of
the 1,3-oxathiolanes was then improved by the promotion of
the reaction of the oxiranes with carbonyl sulfide.
16. Berbero, M.; Degani, I.; Dughera, S.; Fochi, R.; Piscopo, L.
J. Chem. Soc., Perkin Trans. 1 1996, 289.
11. Thioformic acid S-benzyl ester was formed in 2% yield by the
reaction of sulfur with carbon monoxide in the presence of
sodium hydride followed by alkylation with benzyl bromide.
12. Sonoda, N.; Mizuno, T.; Murakami, S.; Kondo, K.; Ogawa, A.;
Ryu, I. Angew. Chem., Int. Ed. Engl. 1989, 28, 452.
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2000, 30, 3081; (b) Mizuno, T.; Kino, T.; Ito, T.; Miyata, T.
Synth. Commun. 2000, 30, 1675; (c) Mizuno, T.; Nishiguchi,
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Soc. Jpn. 1988, 61, 921.
18. Taguchi, Y.; Yasumoto, M.; Shibuya, I.; Suhara, Y. Bull. Chem.
Soc. Jpn. 1989, 62, 474.
19. Foster, R. C.; Owen, L. N. J. Chem. Soc., Perkin Trans. 1 1978,
822.
20. Lalancette, J. M.; Freche, A. Can. J. Chem. 1971, 49, 4047.
21. Takida, T.; Kobayashi, Y.; Itabashi, K. Synthesis 1986, 779.