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M. I. García-Moreno et al. / Tetrahedron: Asymmetry 10 (1999) 4271–4275
Acknowledgements
Support from DGICyT (grant no. PB 97/0747) is acknowledged. M.I.G.M. thanks the Fundación
Cámara for a doctoral fellowship.
References
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Z. J., Ed.; Marcel Dekker Inc.: New York, 1997; pp. 1–37.
12. Johnson, C. R.; Golebiowski, A.; Sundram, H.; Miller, M. W.; Dwaihy, R. L. Tetrahedron Lett. 1994, 36, 653–654.
13. Paulsen, H. Adv. Carbohydr. Chem. Biochem. 1968, 23, 115–232.
14. Jiménez Blanco, J. L.; Ortiz Mellet, C.; Fuentes, J.; García Fernández, J. M. Chem. Commun. 1996, 2077–2078.
15. Jiménez Blanco, J. L.; Ortiz Mellet, C.; Fuentes, J.; García Fernández, J. M. Tetrahedron 1998, 14123–14144.
16. Jiménez Blanco, J. L.; Díaz Pérez, V. M.; Ortiz Mellet, C.; Fuentes, J.; García Fernández, J. M.; Díaz Arribas, J. C.;
Cañada, F. J. Chem. Commun. 1997, 1969–1970.
17. García Fernández, J. M.; Ortiz Mellet, C.; Benito, J. M.; Fuentes, J. Synlett 1998, 316–318.
18. Szarek, W. A.; Jones, J. K. N. Can. J. Chem. 1965, 43, 2345–2356.
19. For a recent review on sugar isothiocyanates and thioureas, see: García Fernández, J. M.; Ortiz Mellet, C. Sulfur Reports
1996, 19, 61–169.
20. For clarity of presentation, the authors chose not to use the numbers resulting from the nomenclature of piperidine
heterocycles in the notation of atoms for NMR data. Instead, the notation is kept consistent with the parent carbohydrate
compounds.
21. All new compounds gave satisfactory microanalytical, MS and spectroscopic data. Data for 10a: [α]2D2=+61.0 (c 1.0,
H2O); δH (D2O, 300 MHz) 3.08 (1H, dd, J4,5b=11.0, J5a,5b=13.0, H-5b), 3.07 (3H, s, OMe), 3.31 (3H, s, NMe), 3.50 (1H,
ddd, J4,5a=5.3, J3,4=9.3, H-4), 3.54 (1H, dd, J1,2=3.3, J2,3=9.3, H-2), 3.69 (1H, t, H-3), 4.15 (1H, dd, H-5a), 6.22 (1H, d,
H-1); δC (D2O, 75.5 MHz) 34.7, 46.8, 57.5, 71.3, 73.4, 6.2, 90.5, 184.6. Data for 10b: [α]2D2=+54.0 (c 1.0, MeOH); δH
(D2O, 500 MHz, 313K) 3.27 (1H, dd, J4,5b=11.0, J5a,5b=13.0, H-5b), 3.45 (3H, s, OMe), 3.66 (1H, ddd, J4,5a=5.5, J3,4=9.3,
H-4), 3.67 (1H, dd, J1,2=3.5, J2,3=9.3, H-2), 3.79 (1H, t, H-3), 4.44 (1H, dd, H-5a), 6.27 (1H, d, H-1), 7.30–7.50 (5H,
m, Ph); δC (D2O, 125.5 MHz, 313K) 45.9, 55.7, 69.2, 70.8, 74.0, 88.8, 126.9, 127.3, 129.4, 139.3, 183.7. Data for 10d:
[α]2D2=+25.4 (c 1.0, H2O); δH (D2O, 500 MHz, 313K) 3.06 (1H, dd, J4,5b=11.3, J5a,5b=13.5, H-5b), 3.25 (3H, s, OMe),
0
3.36 (1H, dd, J4 ,5 =8.5, J3 ,4 =9.5, H-4 ), 3.45 (1H, ddd, J5 ,6 a=2.0, J5 ,6 b=5.0, H-50), 3.45 (1H, m, H-4), 3.46 (1H, dd,
0
0
0
0
0
0
0 0
0
0 0
1,2=3.6, J2,3=9.5, H-2), 3.50 (1H, t, J1 ,2 =J =9.5, H-2 ), 3.53 (1H, t, H-3 ), 3.60 (1H, t, J3,4=9.5, H-3), 3.66 (1H, dd,
2 ,3
0
0
0
0
J
J
6a,6b=12.5, H-60b), 3.79 (1H, dd, H-60a), 4.21 (1H, bs, H-5a), 5.70 (1H, d, H-10), 6.25 (1H, d, H-1); δC (D2O, 125.5 MHz)
44.9, 55.5, 60.7, 68.7, 69.4, 70.5, 71.8, 73.9, 76.7, 77.6, 85.1, 88.8, 184.3.
22. The converse strategy using isothiocyanate 8 in reaction with azides–triphenylphosphine proved less convenient. The
reaction probably involves a sugar phosphazide instead of an iminophosphorane intermediate, as previously observed for
related transformations. See: García Fernández, J. M.; Ortiz Mellet, C.; Díaz Pérez, V. M.; Fuentes, J.; Kovács, J.; Pintér,
J. Carbohydr. Res. 1997, 304, 261–270.
23. García Fernández, J. M.; Ortiz Mellet, C.; Díaz Pérez, V. M.; Fuentes, J.; Kovács, J.; Pintér, J. Tetrahedron Lett. 1997,
4161–4164.