7012
J. S. Yada6 et al. / Tetrahedron Letters 43 (2002) 7009–7012
3. (a) Perez, M.; Beau, J. M. Tetrahedron Lett. 1989, 30, 75;
ethyl acetate (2×15 mL). The combined organic layers
were dried over anhydrous Na2SO4, concentrated in
vacuo and purified by column chromatography on silica
gel (Merck, 100–200 mesh, ethyl acetate–hexane, 1:9) to
afford the pure glycoside. Spectral data for the com-
pounds: 2d (Table 1): [h]2D0 (h-anomer) 124 (c 1.0, CHCl3);
1H NMR (CDCl3, 200 MHz): l 5.87 (m, 1H, CꢀCH),
5.32–5.15 (m, 4H, H-3, H-4, CꢀCH2), 5.04 (bd, 1H,
J=3.0 Hz, H-1), 4.15 (m, 1H, H-5), 4.13 (m, 1H, -OCH),
4.07 (m, 2H, H-6a, 6b), 3.95 (m, 1H, -OCH), 2.11 (s, 3H,
-COCH3), 2.08 (m, 1H, H-2eq), 2.03 (s, 3H, -COCH3),
1.96 (s, 3H, COCH3), 1.88 (m, 1H, H-2ax). 13C NMR (50
MHz): l 20.5, 20.6, 30.1, 62.1, 66.1, 66.5, 66.7, 68.0, 96.0,
96.5, 117.3, 133.6, 169.5, 169.8, 169.9. EIMS: m/z: 330
M+, 273, 213. IR (KBr) w 3339, 3037, 1695, 1531, 1229,
(b) Costantino, V.; Imperatore, C.; Fattorusso, E.; Man-
goni, A. Tetrahedron Lett. 2000, 41, 9177; (c) Ramesh, S.;
Kaila, N.; Grewal, G.; Franck, R. W. J. Org. Chem.
1990, 55, 5; (d) Bock, K.; Lundt, I.; Pedersen, C. Carbo-
hydr. Res. 1984, 130, 125.
4. (a) Takiura, K.; Honda, S. Carbohydr. Res. 1972, 23, 369;
(b) Binkley, R. W.; Bankaitis, D. J. Carbohydr. Chem.
1982, 1, 1; (c) Lin, T. H.; Kovac, P.; Glaudemans, C. P.
J. Carbohydr. Res. 1989, 188, 228.
5. Bolitt, V.; Mioskowski, C.; Lee, S. G.; Falck, J. R. J.
Org. Chem. 1990, 55, 5812.
6. (a) Toshima, K.; Nagai, H.; Ushiki, Y.; Matsumura, S.
Synlett 1998, 1007; (b) Pachamuthu, K.; Vankar, Y. D. J.
Org. Chem. 2001, 66, 7511.
7. (a) Ferrier, R. J.; Prasad, N. J. J. Chem. Soc. C 1969,
570; (b) Ferrier, R. J. Adv. Carbohydr. Chem. Biochem.
1969, 24, 199; (c) Masson, C.; Soto, J.; Bessodes, M.
Synlett 2000, 1281.
978, 729 cm−1
.
2e (Table 1): [h]2D0 (h-anomer) 106 (c 1.0, CHCl3); 1H
NMR (CDCl3, 200 MHz): l 5.25 (m, 1H, H-3) 5.0 (brs,
1H, H-1), 4.90 (t, 1H, J=9.0 Hz, H-4), 4.20 (dd, 1H,
J=4.5, 11.8, H-6a), 3.95 (m, 2H, H-6b, H-5), 3.35 (m,
2H, -OCH2), 2.20 (dd, 1H, J=6.0, 13.5 Hz, H-2eq), 2.10
(s, 3H, -COCH3), 2.08 (s, 3H, COCH3), 1.98 (s, 3H,
-COCH3), 1.78 (ddd, 1H, J=6.0, 11.8, 13.5 Hz, H-2ax),
1.0 (m, 1H, -CH-), 0.5 (m, 2H, -CH2-), 0.18 (m, 2H,
-CH2-). 13C NMR (50 MHz): l 2.9, 3.2, 10.3, 20.6, 20.9,
29.6, 35.1, 62.5, 67.8, 69.2, 69.7, 72.4, 96.5, 169.8, 170.0,
170.5. IR (KBr) w: 3343, 3045, 1700, 1535, 1230, 970, 741
8. Imamoto, T. Lanthanides in Organic Synthesis; Academic
Press: New York, 1994.
9. (a) Cappa, A.; Marcantoni, E.; Torregiani, E.; Bartoli,
G.; Bellucci, M. C.; Bosco, M.; Sambri, L. J. Org. Chem.
1999, 64, 5696; (b) Marcantoni, E.; Nobili, F.; Bartoli,
G.; Bosco, M.; Sambri, L.; Torregiani, E. J. Org. Chem.
1997, 62, 4183; (c) Di Dea, M.; Marcantoni, E.; Torre-
giani, E.; Bartoli, G.; Bellucci, M. C.; Bosco, M.; Sambri,
L. J. Org. Chem. 2000, 65, 2830; (d) Yadav, J. S.; Reddy,
B. V. S. Synlett 2000, 1275; (e) Yadav, J. S.; Reddy, B. V.
S.; Reddy, M. S.; Sabitha, G. Synlett 2001, 1134.
10. Experimental procedure: a mixture of 3,4,6-tri-O-acetyl-
cm−1
.
3a (Table 2): solid, mp 42–43°C; [h]2D0 (h-anomer) 80.4 (c
2.0, CHCl3); 1H NMR (CDCl3, 200 MHz): l 5.83–6.0 (m,
3H, H-2, H-3, H-21), 5.28–5.38 (m, 2H, H-4, H-31b), 5.22
(dq, J=10.4, 1H, H-31a), 5.08 (brs, 1H, H-1), 4.03–4.30
(m, 5H, H-5, H-6a, 6b, H-11a, 11b), 2.08 (s, 6H, COCH3).
13C NMR (CDCl3, 50 MHz): l 20.7, 20.9, 62.9, 65.2,
66.9, 69.2, 93.6, 117.5, 127.7, 129.2, 134.0, 170.2, 170.7.
D
-glucal (5 mmol), the alcohol (10 mmol), CeCl3·7H2O
(7.5 mmol) and NaI (7.5 mmol) in acetonitrile (10 mL)
was stirred at reflux temperature for a specified time as
required to complete the reaction (Table 1). After com-
plete conversion, as indicated by TLC, the reaction mix-
ture was diluted with water (15 mL) and extracted with
IR (KBr) w 3375, 2926, 1733, 1535, 1441 cm−1
.