6110
M. Moghadam et al. / Tetrahedron 60 (2004) 6105–6111
concentrated under reduced pressure and chromatographed
on silica gel column to give the pure product in 93–99%
yields.
s), 1.15(6H, d, J¼6 Hz); IR(neat): 2970, 2930, 2870, 1460,
1380, 1365, 1260, 1125, 1070, 1030, 920, 850, 735 cm21
.
Compound 2f: n2D0¼1.4318 (lit.18e nD20¼1.4320); 1H
NMR(CDCl3) d: 5.95–4.70(3H, m), 4.35–3.32(7H, m),
1.33(3H, s), 1.25(3H, s); IR(neat): 3050, 3000, 2920, 2850,
4.3. General procedure for conversion of epoxides to
thiiranes with NH4SCN or H2NCSNH2
1455, 1360, 1320, 1250, 1090, 920, 840, 755 cm21
.
In a round-bottomed flask (25 mL) equipped with a
condenser and a magnetic stirrer, a solution of epoxide
(1 mmol) in acetonitrile (5 mL) was prepared. Ammonium
thiocyanate or thiourea (2 mmol) and Sn(IV)(tpp)(OTf)2
(20 mg, 0.019 mmol) was added to this solution and the
reaction mixture was stirred magnetically under reflux
conditions. After completion of the reaction (monitored by
GLC), the mixture was directly passed through a short
column of silica-gel (1:1 hexane–ethyl acetate) to remove
the catalyst. Evaporation of the solvent followed by
chromatography on a short column of silica gel gave pure
thiirane; yield 96–99%.
Compound 2g: n1D5¼1.4359 (lit.18f nD15¼1.4357); 1H
NMR(CDCl3) d: 4.34–3.12(5H, m), 1.32(3H, s), 1.21(3H,
s); IR(neat): 2960, 2900, 2860, 1450, 1375, 1250, 1165,
1080, 1025, 935, 870, 740 cm21
.
Acknowledgements
We would like to acknowledge Prof. I. Mohammadpoor-
Baltork for his expert assistance.
4.4. General procedure for conversion of epoxides to 1,3-
dioxolanes
References and notes
In a round-bottomed flask (25 mL) equipped with a
condenser and a magnetic stirrer, a solution of epoxide
(1 mmol) in acetone (5 mL) was prepared.
Sn(IV)(tpp)(OTf)2 (20 mg, 0.019 mmol) was added to this
solution and the reaction mixture was stirred magnetically
under reflux conditions or room temperature. The reaction
progress was monitored by GLC. After completion of the
reaction, the mixture was directly passed through a short
column of silica-gel (1:1 hexane–ethyl acetate) to remove
the catalyst. The elute was evaporated under reduced
pressure and the crude product was obtained in a
quantitative yield. Distillation of product under reduced
pressure resulted in the corresponding 1,3-dioxolane in
88–98% yields.
1. (a) Bonini, C.; Righi, G. Synthesis 1994, 225. (b) Iranpoor, N.;
Mohammadpour-Baltork, I. Synth. Commun. 1990, 20, 2789.
(c) Shimizu, M.; Yoshida, A.; Fujisawa, T. Synlett 1992, 204.
(d) Munavalli, S.; Rohrbaugh, D. K.; Berg, F. J.; Longo, F. R.;
Durst, H. D. Phosphorus, Sulfur Silicon 2002, 177, 215, and
references cited therein.
2. (a) Sharghi, H.; Nasseri Ali, M.; Niknam, K. J. Org. Chem.
2001, 66, 7287. (b) Hodgson, D. M.; Gibbs, A. R.; Lee, G. P.
Tetrahedron 1996, 52, 14361. (c) Paterson, I.; Berrisford, D. J.
Angew. Chem., Int. Ed. Engl 1992, 31, 1197. (d) Taylor, S. K.
Tetrahedron 2000, 56, 1149. (e) Parker, R. E.; Isaacs, N. S.
Chem. Rev. 1959, 59, 737. (f) Smith, J. G. Synthesis 1984, 629.
(g) Rao, A. S.; Paknikar, S. K.; Kirtane, J. G. Tetrahedron
1983, 39, 2323.
3. (a) Olah, G. A.; Fung, A. P.; Mieder, D. Synthesis 1981, 280.
(b) Posner, G. H.; Rogers, D. Z.; Kinzig, C. H.; Gurria, G. M.
Tetrahedron Lett. 1975, 16, 3597. (c) Otera, J.; Yoshida, Y.;
Hirakawa, K. Tetrahedron Lett. 1985, 26, 3219.
4.4.1. Physical and spectral data for 1,3-dioxolanes.
Compound 2a: n2D0¼1.4465 (lit.18a nD20¼1.448); 1H
NMR(CDCl3) d: 4.34–4.05(2H, m), 2.58–2.07(4H, m),
1.35(6H, s), 1.24–1.00(4H, m); IR(neat): 2980, 2930, 2870,
4. (a) Posner, G. H.; Rogers, D. Z. J. Am. Chem. Soc. 1977, 99,
8208. (b) Posner, G. H.; Rogers, D. Z. J. Am. Chem. Soc. 1977,
99, 8214. (c) Chini, M.; Crotti, P.; Favero, L.; Pineschi, M.
Tetrahedron Lett. 1994, 35, 433. (d) Iranpoor, N.;
Mohammadpour-Baltork, I. Tetrahedron Lett. 1990, 31, 735.
(e) Iranpoor, N.; Mohammadpour-Baltork, I.; Shiriny
Zardaloo, F. Tetrahedron 1991, 47, 9861. (f) Cheudary,
B. M.; Sudha, Y. Synth. Commun. 1996, 26, 2989. (g) Iranpoor,
N.; Salehi, P. Synthesis 1994, 1152. (h) Masaki, Y.; Miura, T.;
Ochiai, M. Synlett 1993, 847. (i) Masaki, Y.; Miura, T.;
Ochiai, M. Bull. Chem. Soc. Jpn 1996, 69, 195. (j) Iranpoor,
N.; Tarrian, T.; Movahedi, Z. Synthesis 1996, 1473.
(k) Jacobsen, E. N.; Kakiuchi, F.; Konsler, R. G.; Larrow,
J. F.; Tokunaga, M. Tetrahedron Lett. 1997, 38, 773. (l)
Taniguch, Y.; Tanaka, S.; Kitamura, T.; Fujiwara, Y.
Tetrahedron Lett. 1998, 39, 4559. (m) Iranpoor, N.; Shekarriz,
M.; Shiriny, F. Synth. Commun. 1998, 28, 347. (n)
Mohammadpour-Baltork, I.; Tangestaninejad, S.; Aliyan, H.;
Mirkhani, V. Synth. Commun. 2000, 30, 2365. (o) Mirkani, V.;
Tangestaninejad, S.; Yadollahi, B.; Alipanah, L. Tetrahedron
2003, 59, 8213.
1440, 1355, 1260, 1180, 1080, 960, 885, 835, 780 cm21
.
Compound 2b: n2D0¼1.5270 (lit.18b nD20¼1.5273); 1H
NMR(CDCl3) d: 7.25 (5H, s), 5.00(1H, dd, J¼8 Hz),
4.23(1H, dd, J¼7 Hz), 3.62(1H, dd, J¼6 Hz), 1.48(3H, s),
1.40(3H, s); IR(neat): 3036, 2990, 2870, 1600, 1495, 1450,
1365, 1230, 1150, 1055, 945, 850, 755, 700 cm21
.
Compound 2c: n2D0¼1.2495; 1H NMR(CDCl3) d: 4.20–
3.31(3H, m), 1.72–1.13(16H, m), 0.82(3H, t, J¼7 Hz);
IR(neat): 2970, 2915, 2860, 1460, 1375, 1250, 1160, 1050,
950, 850, 730 cm21
.
Compound 2d: mp 63 8C (lit.18c mp 64–65 8C); 1H
NMR(CDCl3) d: 7.47–6.72(5H, m), 4.65–3.64(5H, m),
1.42(3H, s), 1.30(3H, s); IR(KBr): 3070, 2990, 2920, 1600,
1585, 1490, 1445, 1344, 1240, 1210, 1170, 1035, 910, 810,
747 cm21
.
Compound 2e: n2D0¼1.4170 (lit.18d nD20¼1.4168); 1H
NMR(CDCl3) d: 4.37–3.30(6H, m), 1.37(3H, s), 1.27(3H,
5. (a) Suda, K.; Sashima, M.; Izutsu, M.; Hino, F. J. Chem. Soc.