626
M. North, P. Villuendas
LETTER
Compound 3c
O
IR: nmax = 1061 cm–1. 1H NMR (300 MHz, CDCl3): d = 0.86 (3 H, t,
J = 6.7 Hz), 1.20–1.40 (4 H, m), 1.70–1.90 (2 H, m), 3.64 (1 H, dd,
J = 11.9, 8.0 Hz), 3.89 (1 H, dd, J = 11.9, 5.4 Hz), 4.20–4.40 (1 H,
m, CHS). 13C NMR (125 MHz, CDCl3): d = 13.9, 22.4, 30.5, 33.2,
48.3, 61.0, 228.5. ESI-MS: m/z = 215 [M + Na+]. ESI-HRMS: m/z
calcd for C7H13S3 [M+]: 192.0101; found: 192.0095.
(salen)Al
O Al(salen)
S
R
Bu4NBr
O
S
R
(salen)Al
O
Al(salen)
O
BuBr
+
Bu3N
Compound 3e
CS2
R
IR: nmax = 1068 cm–1. 1H NMR (300 MHz, CDCl3): d = 0.82 (3 H, t,
J = 6.8 Hz), 1.10–1.40 (12 H, m), 1.80–2.00 (2 H, m), 3.65 (1 H, dd,
J = 10.8, 6.1 Hz), 3.88 (1 H, dd, J = 11.0, 6.4 Hz), 4.30–4.40 (1 H,
m). 13C NMR (125 MHz, CDCl3): d = 14.2, 22.7, 28.7, 29.2, 29.3,
29.4, 31.9, 33.6, 48.3, 61.1, 228.1. ESI-MS: m/z = 271 [M + Na+].
ESI-HRMS: m/z calcd for C11H21S3 [MH+]: 249.0805; found:
249.0793.
(salen)Al
Bu3N
O
Al(salen)
O
R
S
S
Scheme 5 Proposed mechanism for 1,3-oxathiolane-2-thione for-
mation
Acknowledgment
The authors thank Newcastle University for financial support.
In conclusion, we have shown that bimetallic alumini-
um(salen) complex 6 in conjunction with tetrabutylam-
monium bromide is an effective catalyst system for the
formation of 1,3-oxathiolane-2-thiones and 1,3-dithio-
lane-2-thiones. The stereochemical and reactivity differ-
ences between cyclic carbonate and cyclic
dithiocarbonate formation can be explained on the basis of
the established mechanism for cyclic carbonate synthesis.
References
(1) For reactions leading to mixtures of compounds 1–5, see:
(a) Taguchi, Y.; Yanagiya, K.; Shibuya, I.; Suhara, Y. Bull.
Chem. Soc. Jpn. 1988, 61, 921. (b) Taguchi, Y.; Yasumoto,
M.; Shibuya, I.; Suhara, Y. Bull. Chem. Soc. Jpn. 1989, 62,
474. (c) Yavari, I.; Ghazanfarpour-Darjani, M.; Hossaini, Z.;
Sabbaghan, M.; Hosseini, N. Synlett 2008, 889.
(2) (a) Kihara, N.; Nakawaki, Y.; Endo, T. J. Org. Chem. 1995,
60, 473. (b) Shen, Y.-M.; Duan, W.-L.; Shi, M. Eur. J. Org.
Chem. 2004, 3080. (c) Wu, J.-Y.; Luo, Z.-B.; Dai, L.-X.;
Hou, X.-L. J. Org. Chem. 2008, 9137. (d) Maggi, R.;
Malmassari, C.; Oro, Ch.; Pela, R.; Sartori, G.; Soldi, L.
Synthesis 2007, 53. (e) Halimehjani, A. Z.; Ebrahimi, F.;
Azizi, N.; Saidi, M. R. J. Heterocycl. Chem. 2009, 46, 347.
(3) For the synthesis of 1,3-oxathiolane-2-thiones using
thiophosgene, see: Jones, F. N.; Andreades, S. J. Org. Chem.
1969, 34, 3011.
Synthesis of 1,3-Oxathiolane-2-thiones and 1,3-Dithiolane-2-
thiones
CS2 (0.18 mL, 2.98 mmol), an epoxide (1.67 mmol), catalyst 6 (74
mg, 0.083 mmol) and TBAB (28 mg, 0.083 mmol) were placed in a
sealed Young flask and stirred at 50 °C or 90 °C for 16 h. Then, the
solution was evaporated and the residue purified by column chro-
matography (CHCl3–hexane, 1:1) to give compounds 1a–k and/or
3a–k.
(4) For a related synthesis of 1,3-dithiolane-2-ones by reaction
of epoxides with trithiocarbonates, see: Barbero, M.;
Degani, I.; Dughera, S.; Fochi, R.; Piscopo, L. J. Chem. Soc.,
Perkin Trans. 1 1996, 289.
Characterisation Data for New Compounds
Compound 1c
IR: nmax = 1191 cm–1. 1H NMR (300 MHz, CDCl3): d = 0.86 (3 H, t,
J = 6.7 Hz), 1.20–1.30 (2 H, m), 1.30–1.50 (2 H, m), 1.50–1.70 (2
H, m), 3.45 (1 H, dd, J = 9.5, 6.2 Hz), 3.60 (1 H, dd, J = 11.0, 6.5
Hz), 5.00–5.20 (1 H, m, CHO). 13C NMR (125 MHz, CDCl3): d =
22.4, 33.5, 36.4, 39.5, 44.1, 92.1, 212.4. ESI-MS: m/z = 199 [M +
Na+]. ESI-HRMS: m/z calcd for C7H13S2O [MH+]: 177.0408; found:
177.0405.
(5) For other syntheses of 1,3-dithiolane-2-ones, see:
(a) Corey, E. J.; Mitra, R. B. J. Am. Chem. Soc. 1962, 84,
2938. (b) Overberger, C. G.; Drucker, A. J. Org. Chem.
1964, 29, 360. (c) Kyaw, M.; Owen, L. N. J. Chem. Soc.
1965, 1298. (d) Adley, T. J.; Anisuzzaman, A. K. M.; Owen,
L. N. J. Chem. Soc. C 1967, 807. (e) Ley, S. V.; Meerholz,
C. A.; Barton, D. H. R. Tetrahedron Lett. 1980, 21, 1785.
(f) Cussans, N. J.; Ley, S. V.; Barton, D. H. R. J. Chem. Soc.,
Perkin Trans. 1 1980, 1650. (g) Yasuda, N.; Yatami, T.;
Ohnuki, T.; Okutsu, M. J. Heterocycl. Chem. 1984, 21,
1845.
(6) (a) Durden, J. A. Jr.; Stansbury, H. A. Jr.; Catlette, W. H.
J. Am. Chem. Soc. 1960, 82, 3082. (b) Hayashi, S.;
Furukawa, M.; Fujino, Y.; Nakao, T.; Nagato, K. Chem.
Pharm. Bull. 1971, 19, 1594. (c) McCasland, G. E.;
Zanlungo, A. B.; Durham, L. J. J. Org. Chem. 1974, 39,
1462. (d) Jesudason, M. V.; Owen, L. N. J. Chem. Soc.,
Perkin Trans. 1 1974, 1443. (e) Motokucho, S.; Takeuchi,
D.; Sanda, F.; Endo, T. Tetrahedron 2001, 57, 7149.
(7) Robbe, Y.; Fernandez, J.-P.; Dubief, R.; Chapat, J.-P.;
Sentenac-Roumanou, H.; Fatome, M.; Laval, J.-D.; Subra,
G. Eur. J. Med. Chem. 1982, 17, 235.
Compound 1j
IR: nmax = 1192 cm–1. 1H NMR (300 MHz, CDCl3): d = 1.40 (3 H,
d, J = 6.7 Hz), 1.51 (3 H, d, J = 6.3 Hz), 3.70–3.80 (1 H, m), 4.70–
4.80 (1 H, m). 13C NMR (125 MHz, CDCl3): d = 17.6, 18.0, 52.5,
93.5, 211.6. ESI-MS: m/z = 171 [M + Na+]. ESI-HRMS: m/z calcd
for C5H8S2ONa [M + Na+]: 170.9914; found 170.9911.
Compound 1k
IR: nmax = 1192 cm–1. 1H NMR (300 MHz, CDCl3): d = 1.32 (3 H,
d, J = 6.7 Hz), 1.46 (3 H, d, J = 6.7 Hz), 3.80–3.90 (1 H, m), 5.10–
5.20 (1 H, m). 13C NMR (125 MHz, CDCl3): d = 14.7, 15.6, 49.5,
89.8, 212.0. ESI-MS: m/z = 171 [M + Na+]. ESI-HRMS: m/z calcd
for C5H8S2ONa [M + Na+]: 170.9914; found 170.9906.
Synlett 2010, No. 4, 623–627 © Thieme Stuttgart · New York