686
S. Silva et al. / Tetrahedron Letters 49 (2008) 682–686
ˇ
11. (a) Girniene, J.; Apremont, G.; Tatiboue¨t, A.; Sacˇkus, A.; Rollin, P.
tionship to the anomeric oxygen (Fig. 1) might bring an
additional limitation to the construction of a fused OZT.
In summary, we have reported for the first time the
installation on carbohydrate templates of hemiaminals
derived from the parent 4-hydroxy-1,3-oxazolidine-2-thi-
one. Preliminary studies on the reactivity of these carbohy-
drate-fused OZT are ongoing and will be published in due
course.
Tetrahedron 2004, 60, 2609–2619; (b) Girniene, J.; Tardy, S.;
Tatiboue¨t, A.; Sacˇkus, A.; Rollin, P. Tetrahedron Lett. 2004, 45,
ˇ
6443–6446; (c) Leconte, N.; Pellegatti, L.; Xavier, N.; Tatiboue¨t, A.;
Suzenet, F.; Rollin, P.; Guillaumet, G. Synthesis 2007, 857–864.
12. Method A: uloside 4 (0.13 g, 0.35 mmol) and KSCN (0.14 g, 4.1 equiv)
were dissolved in EtOH (10 mL). After cooling at ꢁ5 °C, 12 M
aqueous HCl (0.06 mL, 2.1 equiv) was carefully added and the
mixture was stirred under reflux for 4 h, then cooled by treating with
crushed ice. After extraction with ethyl acetate (3 ꢂ 20 mL), the
combined organic phases were washed first with saturated aqueous
NaHCO3, then water, brine, and finally dried over MgSO4. After
filtration and concentration in vacuo, the residue was purified by
column chromatography (petroleum ether/AcOEt 7:3) to afford
compound 5 (0.088 g, 81% yield) as a white solid. Method B: uloside
4 (0.1 g, 0.27 mmol) and KSCN (0.064 g, 2.4 equiv) were dissolved in
4:1 THF–DMF (10 mL). After cooling at ꢁ5 °C, TsOHꢀH2O (0.107 g,
2.1 equiv) was added and the mixture was stirred overnight under
reflux, then cooled by treating with crushed ice. After extraction with
ethyl acetate (3 ꢂ 20 mL), the combined organic phases were
processed as in method A: compound 5 (0.075 g, 89% yield) was
Acknowledgments
The authors wish to thank the PESSOA program, the
´
´
Universite d’Orleans, the Universidade de Lisboa for finan-
cial support and the FCT for fellowships (S.S. and A.C.S.).
References and notes
20
1. (a) Leoni, O.; Bernardi, R.; Gueyrard, D.; Rollin, P.; Palmieri, S.
Tetrahedron: Asymmetry 1999, 10, 4775–4780; (b) Gueyrard, D.;
Grumel, V.; Leoni, O.; Palmieri, S.; Rollin, P. Heterocycles 2000, 52,
827–843; (c) Gardiner, J. B.; Morra, M. J.; Eberlein, C. V.; Brown, P.
D.; Borek, V. J. Agric. Food. Chem. 1999, 47, 3837–3842; (d) Li, G.;
Qian, X.; Cui, J.; Huang, Q.; Zhang, R.; Guan, H. J. Agric. Food.
Chem. 2006, 54, 125–129; (e) Van Daele, I.; Munier-Lehmann, H.;
Hendrickx, P. M. S.; Marchal, G.; Chavarot, P.; Froeyen, M.; Quing,
L.; Martins, J. C.; Van Calenbergh, S. ChemMedChem 2006, 1, 1081–
1090; (f) Velazquez, F.; Olivio, H. F. Curr. Org. Chem. 2002, 6, 1–38;
(g) Garcia-Fernandez, J. M.; Ortiz-Mellet, C. Adv. Carbohydr. Chem.
Biochem. 2000, 55, 35–135.
obtained in the form of a white solid, mp 156–158 °C; ½aꢃD ꢁ4 (c 0.3,
MeOH). 1H NMR (400 MHz, MeOH) d 3.36 (s, 3H, Me), 3.64–3.79
(m, 2H, J5a–5b = 10.6 Hz, H-5a, H-5b), 4.31 (dd, 1H, J4–5a = 5.0 Hz,
J4–5b = 8.4 Hz, H-4), 4.52–4.59 (AB system, 2H, J6a–6b = 12.0 Hz,
CH2Ph), 4.72 (s, 1H, H-2), 4.99 (s, 1H, H-1), 7.28–7.36 (m, 5H, H-Ar).
13C NMR (100 MHz, MeOH) d 55.5 (OMe), 71.8 (C-5), 74.4
(CH2Ph), 86.1 (C-4), 95.5 (C-2), 98.7 (C-3), 109.3 (C-1), 128.8,
129.1, 129.4 (CH-Ar), 139.3 (CIV-Ar), 189.3 (C@S). MS (IS+): m/z =
280 [MꢁMeOH+H]+, 312.5 [M+H]+, 334.5 [M+Na]+.
´
13. Rauter, A. P.; Fernandes, A. C.; Czernecki, S.; Valery, J. -M. J. Org.
Chem. 1996, 61, 3594–3598; and references cited therein.
14. (a) Chery, F.; De Lucchi, O.; Cossu, S.; Rollin, P. Synthesis 2001,
´
2. (a) Crimmins, M. T.; King, B. W.; Tabet, E. A.; Chaudhary, K. J. Org.
Chem. 2001, 66, 894–902; (b) Guz, N. R.; Phillips, A. J. Org. Lett. 2002,
4, 2253–2256; (c) Crimmins, M. T.; McDougall, P. J. Org. Lett. 2003, 5,
591–594; (d) Zhang, W.; Carter, R. G.; Yokochi, A. F. T. J. Org. Chem.
2004, 69, 2569–2572; (e) Jalce, G.; Seck, M.; Franck, X.; Hocquemiller,
286–292; (b) Chevalier-du Roizel, B.; Cabianca, E.; Rollin, P.; Sinay,
¨
P. Tetrahedron 2002, 58, 9579–9583; (c) Uttaro, J.-P.; Uttaro, L.;
´
´
Tatiboue¨t, A.; Rollin, P.; Mathe, C.; Perigaud, C. Tetrahedron Lett.
2007, 48, 3851–3854.
15. Uloside 14 (0.62 g, 1.3 mmol) and KSCN (0.51 g, 4 equiv) were
dissolved in 4:1 THF–DMF (30 mL). After cooling at ꢁ5 °C,
TsOHꢀH2O (0.74 g, 3 equiv) was carefully added and the mixture
was stirred under reflux for 24 h, then cooled by treating with crushed
ice. After extraction with ethyl acetate (3 ꢂ 50 mL), the combined
organic phases were processed as in method A: compound 16 (0.48 g,
`
R.; Figadere, B. J. Org. Chem. 2004, 69, 3240–3241; (f) Kocienski, P. J.;
Stocks, M.; Donald, D.; Perry, M. Synlett 1990, 38–39; (g) Brown, R.
C. D.; Kocienski, P. J. Synlett 1994, 415–417; (h) Crimmins, M. T.;
Katz, J. D.; Washburn, D. G.; Allwein, S. P.; McAtee, L. F. J. Am.
Chem. Soc. 2002, 124, 5661–5663; (i) Chakraborty, T. K.; Jayaprakash,
S.; Laxman, P. Tetrahedron 2001, 57, 9461–9467.
20
88% yield) was obtained as a white solid, mp 74–75 °C; ½aꢃD ꢁ118 (c
1, CHCl3). 1H NMR (400 MHz, CDCl3) d 3.36 (dt, 1H, J5–6a
=
3. (a) Willems, J. F.; Vandenberghe, A. Bull. Soc. Chim. Belg. 1961, 70,
745–748; (b) Lacasse, G.; Muchowki, J. M. Can. J. Chem. 1972, 50,
3082–3083.
4. (a) Bradscher, C. K.; Jones, W. J. J. Org. Chem. 1967, 32, 2079–2081;
(b) Guimon, C.; Pfister-Guillouzo, G.; Arbelot, M.; Chanon, M.
Tetrahedron 1974, 30, 3831–3838; (c) Kapsomenos, G. S.; Akrivos, P.
D. D. Can. J. Chem. 1988, 66, 2835–2838; (d) Shafer, C. M.; Molinski,
T. F. J. Org. Chem. 1998, 63, 551–555.
5. Gonzalez-Romero, C.; Martinez-Palou, R.; Jimenez-Vazquez, H. A.;
Fuentes, A.; Jimenez, F.; Tamariz, J. Heterocycles 2007, 71, 305–321.
6. Bobosik, V.; Piklerova, A.; Maretvon, A. Coll. Czech. Chem.
Commun. 1983, 48, 3421–3425.
7. (a) Tatiboue¨t, A.; Lawrence, S.; Rollin, P.; Holman, G. D. Synlett
2004, 1945–1948; (b) Leconte, N.; Silva, S.; Tatiboue¨t, A.; Rauter, A.
P.; Rollin, P. Synlett 2006, 301–305.
5.1 Hz, J5–6b = 9.9 Hz, J5–4 = 10.0 Hz, H-5), 3.47–3.51 (m, 2H, H-8),
3.54 (s, 3H, Me), 3.55–3.57 (m, 2H, H-6b, H-4), 4.20 (dd, 1H,
J6a–6b = 10.7 Hz, J6a–5 = 5.1 Hz, H-6a), 4.52 (d, 1H, J3–4 = 7.5 Hz,
H-3), 4.62 (s, 1H, H-1), 4.86 (br s, 1H, OH), 5.00 (t, J7–8 = 5.0 Hz,
H-7), 7.60–7.63 (m, 2H, meta-H-Ar), 7.66–7.70 (m, 1H, para-H-Ar),
7.91–7.93 (m, 2H, ortho-H-Ar), 8.11 (br s, 1H, N–H). 13C NMR
(100 MHz, CDCl3): d 57.9 (OMe), 59.7 (C-8), 63.3 (C-5), 68.4 (C-6),
78.8 (C-4), 87.3 (C-3), 88.1 (C-2), 97.1 (C-7), 101.9 (C-1), 128.6 (CH-
ortho-Ph), 129.5 (CH-meta-Ph), 134.3 (CH-para-Ph), 139.2 (CIV-Ar),
189.0 (C@S). MS (IS+): m/z = 418.5 [M+H]+, 440.5 [M+Na]+.
16. See for example: Liu, H.- M.; Sato, Y.; Tsuda, Y. Chem. Pharm. Bull.
1993, 41, 491–501.
17. Saito, Y.; Zevaco, T. A.; Agrofoglio, L. A. Tetrahedron 2002, 58,
9593–9603.
`
`
8. Moravcova, J.; Capkova, J.; Stanek, J. Carbohydr. Res. 1994, 263,
18. Silva, S.; Tatiboue¨t, A.; Rauter, A. P.; Justino, J.; Rollin, P.
unpublished results.
61–66.
9. David, S.; Hanessian, S. Tetrahedron 1985, 41, 643–663.
10. Liptak, A.; Neszmelyi, A.; Kovac, P.; Hirsch, J. Tetrahedron 1981, 37,
2379–2382.
19. The configuration of hemiaminal stereogenic centers was assigned
through NOESY experiments. All OZTs showed
relationship.
a strict cis