L. Ying, J. Gervay-Hague / Carbohydrate Research 339 (2004) 367–375
373
CH2), 4.38 (d, J 8.5 Hz, 1H, H-10), 4.68 (d, J 8.5 Hz, 1H,
H-1), 7.20 (app-t, 2H, Fmoc-Ar), 7.28 (app-t, 2H,
Fmoc-Ar), 7.57 (d, J 7.5 Hz, 2H, Fmoc-Ar), 7.68 (d, J
7.5 Hz, 2H, Fmoc-Ar). 13C NMR (CD3OD, 125 MHz):
d 48.3 (Fmoc-CH), 68.2 (Fmoc-CH2), 72.9, 73.0, 74.6
(C-20), 76.1, 76.3, 76.8, 77.1, 81.9 (C-4), 84.0 (C-1), 104.4
(C-10), 120.9, 126.3, 128.2, 128.8, 142.6, 145.2, 158.8,
171.8, 172.3. HRFABMS: calcd for C27H29NO14Na
[M+Na]þ 614.1477, found 614.1457.
H-5), 3.60–3.69 (m, 5H, H-20, H-30, H-6, H-600 , H-60),
3.80–3.87 (m, 3H, H-40, H-50, H-60), 4.14–4.36 (m, 3H,
Fmoc-CH, Fmoc-CH2), 4.63 (d, J 9.0 Hz, 1H, H-1), 4.80
(1H, H-10), 7.25 (app-t, 2H, Fmoc-Ar), 7.32 (app-t, 2H,
Fmoc-Ar), 7.60 (d, J 7.5 Hz, 2H, Fmoc-Ar), 7.72 (d, J
7.5 Hz, 2H, Fmoc-Ar). 13C NMR (CD3OD, 125 MHz): d
48.2 (Fmoc-CH), 62.8 (C-60), 67.6 (C-6), 68.0 (Fmoc-
CH2), 70.5, 71.2, 71.4, 71.6, 72.3, 73.6, 78.0, 79.0, 83.9
(C-1), 100.3 (C-10), 120.9, 126.1, 128.2, 128.8, 142.6,
145.2, 158.7. ESIMS: calcd for C27H33NO12Na
[M+Na]þ 586.2, found 586.2.
4.15. b-
D
-Galactopyranosyl-(1 fi 4)-N-(fluoren-9-yl-
-glucopyranosylamine (22)
methoxycarbonyl)-b-
D
4.18. a-
ren-9-ylmethoxycarbonyl)-b-
D
-Galactopyranosyluronic acid-(1 fi 6)-N-(fluo-
-glucopyranosylamine (27)
A white powder was obtained in 18% yield from 20 and
34% from 21. 1H NMR (DMSO, 500 MHz): d 3.11 (t, J
9.0 Hz, 1H, H-2), 3.20–3.28 (m, 5H, H-20, H-30, H-3,
H-4, H-5), 3.39–3.63 (m, 6H, H-40, H-50, H-6, H-60,
H-600 , H-60), 4.14–4.28 (m, 4H, H-10, Fmoc-CH, Fmoc-
CH2), 4.46 (d, J 9.0 Hz, 1H, H-1), 7.27 (app-t, 2H,
Fmoc-Ar), 7.35 (app-t, 2H, Fmoc-Ar), 7.65 (m, 2H,
Fmoc-Ar), 7.81 (d, J 7.5 Hz, 2H, Fmoc-Ar). 13C NMR
(DMSO, 125 MHz): d 47.0 (Fmoc-CH), 60.5 (C-6), 60.9
(C-60), 66.3 (Fmoc-CH2), 68.6 (C-40), 71.0 (C-20), 71.9
(C-2), 73.4, 75.9 (2C), 76.6, 80.5, 82.5 (C-1), 104.1 (C-10),
120.7, 125.7, 125.8, 127.8, 128.3, 141.2, 144.1, 144.3,
156.8. ESIMS: calcd for C27H33NO12Na [M+Na]þ
586.2, found 586.2.
D
A white powder was obtained with yield 64% from 26.
25
D
½aꢁ )40.1ꢁ (c 0.7, CH3OH). 1H NMR (DMSO,
500 MHz): d 3.11 (m, 2H, H-2, H-4), 3.19 (t, J 9.0 Hz,
1H, H-3), 3.29 (m, 1H, H-5), 3.51–3.63 (m, 4H, H-20, H-
30, H-6, H-60), 3.99 (s, 1H, H-50), 4.21–4.34 (m, 4H, H-40,
Fmoc-CH, Fmoc-CH2), 4.46 (d, J 9.0 Hz, 1H, H-1), 4.72
(d, J 2.5 Hz, 1H, H-10), 7.32 (app-t, 2H, Fmoc-Ar), 7.40
(app-t, 2H, Fmoc-Ar), 7.68 (m, 2H, Fmoc-Ar), 7.85 (d,
J 7.5 Hz, 2H, Fmoc-Ar). 13C NMR (DMSO, 125 MHz):
d 47.0 (Fmoc-CH), 66.5 (Fmoc-CH2), 66.6 (C-6), 68.1,
69.2, 70.1, 70.6, 70.7, 72.2, 76.6 (C-5), 77.7 (C-3), 82.9
(C-1), 98.8 (C-10), 120.7, 125.8, 125.9, 127.8, 128.4,
141.2, 141.2, 144.2, 144.4, 156.7, 171.1. HRFABMS:
calcd for C27H31NO13Na [M+Na]þ 600.1684, found
600.1711.
4.16. b- -Galactopyranosyl-(1 fi 4)-N-(fluoren-9-yl-
D
methoxycarbonyl)-b-D-glucopyranosylamine uronic
acid (23)
4.19. N-(Fluoren-9-ylmethoxycarbonyl)-C-(b-D-galacto-
pyranosyluronic acid)methylamine
25
D
A white powder was obtained in 68% yield from 22. ½aꢁ
1
)12.0ꢁ (c 1.0, CH3OH). H NMR (CD3OD, 500 MHz):
d 3.31 (t, J 9.0 Hz, 1H, H-2), 3.49 (m, 2H, H-20, H-30),
3.55 (t, J 9.0 Hz, 1H, H-3), 3.65 (t, J 9.0 Hz, 1H, H-4),
3.94 (d, J 9.0 Hz, 1H, H-5), 4.09 (s, 1H, H-40), 4.15 (t, J
7.0 Hz, 1H, Fmoc-CH), 4.21 (s, 1H, H-50), 4.29 (m, 2H,
Fmoc-CH2), 3.39–3.63 (m, 6H, H-40, H-50, H-6, H-60, H-
600 , H-60), 4.30–4.33 (m, 3H, H-10, Fmoc-CH2), 4.72 (d, J
9.0 Hz, 1H, H-1), 7.22 (app-t, 2H, Fmoc-Ar), 7.30 (app-
t, 2H, Fmoc-Ar), 7.59 (d, J 7.5 Hz, 2H, Fmoc-Ar), 7.70
(d, J 7.5 Hz, 2H, Fmoc-Ar). 13C NMR (CD3 OD,
125 MHz): d 48.3 (Fmoc-CH), 68.2 (Fmoc-CH2), 71.1
(C-40), 71.8 (C-20), 73.0 (C-2), 74.1 (C-50), 76.7 (C-5),
77.0 (C-30), 82.3 (C-4), 83.8 (C-1), 104.6 (C-10), 120.9,
126.2, 128.2, 128.8, 142.6, 145.2, 158.7, 171.6, 172.4.
HRFABMS: calcd for C27H29NO14Na [M+Na]þ
614.1477, found 614.1476.
A white powder was obtained in 30% over yield from 5.
1H NMR (CD3OD, 500 MHz): d 3.17 (m, 1H, H-1), 3.22
(m, 1H, CH2), 3.41 (t, J 9.0 Hz, 1H, H-2), 3.46 (dd, J
3.5, 9.0 Hz, 1H, H-3), 3.63 (m, 1H, CH2), 4.11–4.16 (m,
3H, H-4, H-5, Fmoc-CH), 4.31 (m, 2H, Fmoc-CH2),
7.16 (app-t, 2H, Fmoc-Ar), 7.24 (app-t, 2H, Fmoc-Ar),
7.51 (d, J 7.5 Hz, 2H, Fmoc-Ar), 7.64 (d, J 7.5 Hz, 2H,
Fmoc-Ar). 13C NMR (CD3OD, 125 MHz): d 43.0
(CH2), 48.4 (Fmoc-CH), 67.7 (Fmoc-CH2), 69.3 (C-2),
71.7 (C-4), 75.5 (C-3), 78.6 (C-5), 80.3 (C-1), 120.9,
126.2, 128.1, 128.7, 142.6, 145.3, 145.3, 159.1, 173.0
(C-6). HRFABMS: calcd for C22H22NO8Na2
[M+2Na)H]þ 474.1135, found 474.1184.
4.20. Methyl 3,4,6-tri-O-acetyl-2-deoxy-2-(fluoren-9-yl-
-glucopyranoside (31a,b)
methoxycarbonylamino)-a,b-
D
4.17. a-
ylmethoxycarbonyl)-b-
D
-Galactopyranosyl-(1 fi 6)-N-(fluoren-9-
-glucopyranosylamine (26)
D
AcBr (20 mL) was slowly added to
D
-glucosamine
hydrochloride (3 g, 13.9 mmol) under argon. The flask
was tightly sealed and stirred overnight at room tem-
perature. The a-glucosyl bromide crystallized out of
solution, the excess AcBr was removed by filtration, and
A white powder was obtained in 14% yield from 24 and
30% from 25. 1H NMR (CD3OD, 500 MHz): d 3.20 (t, J
9.0 Hz, 1H, H-2), 3.33 (m, 2H, H-3, H-4), 3.43 (m, 1H,