Â
L. Kovacs et al. / Tetrahedron 57 62001) 4609±4621
4616
dd, J5.7, 7.5 Hz, H-1), 5.42 81H, Ct, J9.4, 10.2 Hz,
H-3), 5.20 81H, dd, J5.7, 10.2 Hz, H-2), 5.07 81H, Ct,
J9.4, 10.0 Hz, H-4), 4.26 81H, dd, J4.8, 12.4 Hz, H-6),
4.08 81H, dd, J2.4, 12.4 Hz, H-60), 3.93 81H, ddd, J2.4,
4.8, 10.0 Hz, H-5), 2.18, 2.12, 2.09, 2.04 84£3H, s, CH3);
13C NMR 8CDCl3) d 8ppm): 170.8, 170.5, 169.3, 169.2
8acetyl CO), 157.8 8q, J38.5 Hz, NHCO), 115.4 8q,
J288.0 Hz, CF3), 74.9 8C-1), 69.7 8C-3), 69.1 8C-5), 68.2
8C-2), 68.0 8C-4), 61.6 8C-6), 20.6, 20.5, 20.4, 20.3 8acetyl
Me). Anal. Calcd for C16H20F3NO10 8443.27): C: 43.35, H:
4.55, N: 3.16. Found: C: 43.14, H: 4.42, N: 3.03.
with pivalic anhydride according to General procedure B;
yield: 0.02 g, 5%, colourless crystalline product 8E: ethyl-
acetate±hexane, 5:12), mp 195±1968C, [a]d193.1 8c 1.0,
CHCl3); Rf0.36 8eluent A). nmax 8KBr): 3439, 2362, 1749,
1631, 1365 cm21; 1H NMR 8CDCl3): d 8ppm): 6.65 81H, d,
J7.4 Hz, NH), 5.87 81H, dd, J5.6, 7.4 Hz, H-1), 5.41
81H, t, J9.9 Hz, H-3), 5.10 81 h, dd, J5.6, 9.9 Hz, H-2),
5.07 81H, Ct, J9.9, 10.0 Hz, H-4), 4.29 81H, dd, J4.4,
12.3 Hz, H-6), 4.04 81H, dd, J2.3, 12.3 Hz, H-60), 3.89
81H, m, H-5), 2.09, 2.04 84£3H, s, CH3), 1.15 89H, s,
tBu); 13C NMR 8CDCl3) d 8ppm): 176.3 8NHCO), 170.8,
170.6, 170.5, 169.3 8acetyl CO), 74.3 8C-1), 70.0 8C-3), 68.2
8C-2 and C-4), 68.1 8C-5), 61.8 8C-6), 38.7 8CMe3), 26.7
8C8CH3)3), 23.2, 20.7, 20.5, 20.5 8acetyl Me). Anal. Calcd
for C19H29NO10 8431.44): C: 52.89, H: 6.78, N: 3.25. Found:
C: 52.95, H: 6.89, N: 3.01.
4.4.5. 1-N-Trichloroacetyl-ꢀ2,3,4,6-tetra-O-acetyl-a-d-
glucopyranosyl)-amine ꢀ15). Prepared from 2 80.38 g,
1.00 mmol) with trichloroacetic anhydride according to
General procedure B; yield: 0.34 g, 69%, colourless crystal-
line product 8D: diethylether±hexane), mp 153±1558C,
[a]d196.2 8c 1.1, CHCl3); Rf0.64 8eluent A). nmax
4.4.9. 1-N-ꢀ2,3,4,5,6-Penta-O-acetyl-d-galactonoyl)-
ꢀ2,3,4,6-tetra-O-acetyl-b-d-glucopyranosyl)-amine ꢀ19).
Prepared from 1 80.20 g, 0.54 mmol) with 2,3,4,5,6-penta-
O-acetyl-d-galactonoyl chloride33 according to General
procedure B; yield: 0.33 g, 84%, crystalline colourless
product 8D: ethanol), mp 188±1898C, [a]d151.7 8c 1.0,
CHCl3); Rf0.33 8eluent A). nmax 8KBr): 3428, 2342, 1754,
1652, 1372 cm21; 1H NMR 8CDCl3): d 8ppm): 6.76 81H, d,
J9.6 Hz, NH), 5.67 81H, dd, J2.0, 10.1 Hz, H-30), 5.34
81H, dd, J1.9, 10.1 Hz, H-40), 5.27 8t, J9.7 Hz, H-3),
5.20 81H, m, H-50), 5.12 81H, d, J2.0 Hz, H-20), 5.09
81H, t, J9.6 Hz, H-1), 4.98 81H, t, J9.7 Hz, H-4), 4.85
81H, Ct, J9.6, 9.7 Hz, H-2), 4.22 82H, m, H-6a, H-60a),
4.00 81H, dd, J2.0, 12.5 Hz, H-6b), 3.83 81H, dd, J7.3,
11.5 Hz, H-60b), 3.77 81H, ddd, J2.0, 4.6, 9.7 Hz, H-5),
2.25, 2.09, 2.08, 2.06, 2.04, 2.03, 2.01, 2.01, 1.98 89£3H, s,
CH3); 13C NMR 8CDCl3) d 8ppm): 171.7, 170.4, 170.3,
170.3, 169.9, 169.6, 169.6, 169.5, 168.4 8acetyl CO),
167.3 8NHCO), 77.6 8C-1), 73.6 8C-5), 72.0 8C-3), 71.2
8C-20), 70.0 8C-2), 68.1 8C-4), 67.5 8C-30), 67.2 8C-40),
67.1 8C-50), 61.8 8C-60), 61.5 8C-6), 20.6, 20.5, 20.4, 20.4,
19.9 8acetyl Me). Anal. Calcd for C30H41NO20 8735.65): C:
48.98, H: 5.62, N: 1.90. Found: C: 49.12, H: 5.49, N: 1.94.
8KBr): 3420, 2345, 1761, 1619, 1359 cm21 1H NMR
;
8CDCl3): d 8ppm): 7.24 81H, d, J6.9 Hz, NH), 5.82 81H,
dd, J5.5, 6.9 Hz, H-1), 5.32 81H, dd, J9.1, 10.0 Hz, H-3),
5.22 81H, dd, J5.5, 10.0 Hz, H-2), 5.06 81H, dd, J9.1,
9.9 Hz, H-4), 4.29 81H, dd, J4.7, 12.3 Hz, H-6), 4.10 81H,
dd, J2.3, 12.3 Hz, H-60), 3.92 81H, ddd, J2.3, 4.7,
9.9 Hz, H-5), 2.08, 2.06, 2.04, 2.00 84£3H, s, CH3); 13C
NMR 8CDCl3) d 8ppm): 170.6, 170.1, 169.3, 168.9 8acetyl
CO), 161.9 8NHCO), 92.0 8CCl3), 76.1 8C-1), 69.8 8C-3),
68.9 8C-5), 68.3 8C-2), 68.0 8C-4), 61.5 8C-6), 20.7, 20.6,
20.5, 20.4 8acetyl Me). Anal. Calcd for C16H20Cl3NO10
8492.69): C: 39.01, H: 4.09, N: 2.84. Found: C: 39.22, H:
4.23, N: 2.91.
4.4.6. 1-N-Acetyl-ꢀ2,3,4,6-tetra-O-acetyl-b-d-glucopy-
ranosyl)-amine ꢀ16). Prepared from 1 80.36 g, 0.96 mmol)
with acetic anhydride according to General procedure B;
yield: 0.28 g, 72%, crystalline product 8D: ethylacetate±
hexane), mp 155±1578C, [a]d116.5 8c 1.0, CHCl3),
[lit.32 mp 161±1628C, [a]d117 8c 1.0, CHCl3)];
1
Rf0.22 8eluent A). This compound was identi®ed by H
and 13C NMR.32
4.4.7. 1-N-Pivaloyl-ꢀ2,3,4,6-tetra-O-acetyl-b-d-glucopy-
ranosyl)-amine ꢀ17). Prepared from 1 80.38 g, 1.02 mmol)
with pivalic anhydride according to General procedure B;
yield: 0.09 g, 21%, colourless crystalline product 8E: ethyl-
acetate±hexane, 5:12), mp 148±1508C, [a]d122.1 8c 1.0,
CHCl3); Rf0.46 8eluent A). nmax 8KBr): 3404, 2358, 1750,
1662, 1372 cm21; 1H NMR 8CDCl3): d 8ppm): 6.42 81H, d,
J9.3 Hz, NH), 5.29 81H, Ct, J9.6, 9.7 Hz, H-3), 5.20
81H, Ct, J9.3, 9.4 Hz, H-1), 5.03 81H, Ct, J9.7,
10.0 Hz, H-4), 4.91 81H, Ct, J9.4, 9.6 Hz, H-2), 4.29
81H, dd, J4.2, 12.5 Hz, H-6), 4.03 81H, dd, J2.1,
12.5 Hz, H-60), 3.79 81H, ddd, J2.1, 4.2, 10.0 Hz, H-5),
4.4.10. 1-N-ꢀ2,3,4,5,6-Penta-O-acetyl-d-gluconoyl)-
ꢀ2,3,4,6-tetra-O-acetyl-a-d-glucopyranosyl)-amine ꢀ20).
Prepared from 1 80.20 g, 0.54 mmol) with 2,3,4,5,6-penta-
O-acetyl-d-gluconoyl chloride33 according to General
procedure B; yield: 0.22 g, 55%, colourless crystalline
product 8E: ethanol), mp 153±1558C, [a]d136.5 8c 1.0,
CHCl3); Rf0.21 8eluent A). nmax 8KBr): 3430, 2360, 1756,
1652, 1374 cm21; 1H NMR 8CDCl3): d 8ppm): 6.79 81H, d,
J9.5 Hz, NH), 5.69 81H, dd, J3.0, 6.7 Hz, H-30), 5.45
81H, dd, J4.9, 6.7 Hz, H-40), 5.34 81H, d, J3.0 Hz, H-20),
5.28 81H, Ct, J9.5, 9.6 Hz, H-3), 5.11 81H, Ct, J9.5,
9.6 Hz, H-1), 5.00 81H, t, J9.6, 10.1 Hz, H-4), 4.94 81H,
q, J4.9, 5.2, 5.4 Hz, H-50), 4.88 81H, Ct, J9.5, 9.6 Hz,
H-2), 4.31 81H, dd, J5.2, 12.0 Hz, H-60a), 4.24 81H, dd,
J4.7, 12.5 Hz, H-6a), 4.14 81H, dd, J5.4,12.0 Hz, H-
60b), 4.03 81H, dd, J2.1, 12.5 Hz, H-6b), 3.79 81H, ddd,
J2.1, 4.7, 10.1 Hz, H-5), 2.31, 2.10, 2.08, 2.05, 2.04, 2.03,
2.01, 2.00, 1.98 89£3H, s, CH3); 13C NMR 8CDCl3) d 8ppm):
171.7, 170.5, 170.4, 170.0, 169.7, 169.6, 168.9 8acetyl CO),
167.2 8NHCO), 77.8 8C-1), 73.6 8C-5), 72.5 8C-20), 72.1
8C-3), 69.9 8C-2), 69.7 8C-40), 68.9 8C-30), 68.6 8C-50),
68.1 8C-4), 61.6 8C-6), 61.0 8C-60), 20.5, 20.5, 20.4, 20.3,
2.04, 1.99, 1.98, 1.98 84£3H, s, CH3), 1.12 89H, s, tBu); 13
C
NMR 8CDCl3) d 8ppm): 178.6 8NHCO), 171.0, 170.6,
169.8, 169.5 8acetyl CO), 78.5 8C-1), 73.5 8C-5), 72.5
8C-3), 70.6 8C-2), 68.2 8C-4), 61.6 8C-6), 38.7 8CMe3),
27.0 8C8CH3)3) 20.7, 20.5, 20.5 8acetyl Me). Anal. Calcd
for C19H29NO10 8431.44): C: 52.89, H: 6.78, N: 3.25.
Found: C: 53.00, H: 6.55, N: 3.12.
4.4.8. 1-N-Pivaloyl-ꢀ2,3,4,6-tetra-O-acetyl-a-d-glucopy-
ranosyl)-amine ꢀ18). Prepared from 2 80.38 g, 1.02 mmol)