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G. Baisch, R. Ohrlein/Carbohydrate Research 312 (1998) 61±72
70
ꢃ 103.8, 70.0, 75.5, 68.5, 75.5, 62.2*; Neu5Ac (from
C-1 to C-9, HNCOCH3): ꢃ C-1 not resolved, C-2
not resolved, 40.4, 68.8, 52.9, 73.7, 69.4, 72.0, 63.7,
C O not resolved, 21.4; GalA (from C-1 to C-6,
OCH3): ꢃ 100.9, 68.8, 70.3, 70.6, 72.3, C-6 not
resolved, 55.2; aglycon: ꢃ C O not resolved, 34.1,
25.2, 29.1, 26.1, 29.6, 69.4, 51.2. MS Calcd for
C40H68N2O26: 992; Found [M H]- 991.
3.74, 3.42, 3.91; Gal (from H-1 to H-6a,6b): ꢃ 4.61
(d, 1 H, J1,2 & 7.4 Hz), 3.52, 3.89, 3.90, 3.41, 3.63,
3.76; Neu5Ac (from H-3ax,3eq to H-9a,9b,
HNCOCH3): ꢃ 1.87 (t, 1 H, J3ax,4 & 12.1 Hz), 2.72
(dd, 1 H, J3eq,4 & Hz, J3ax,3eq & 12.1 Hz), 3.72*,
3.74, 3.65, 3.56, 3.74, 3.65, 3.87, 2.02; Fuc (from H-
1 to H-6): ꢃ 5.05 (d, 1 H, J1,2 & 3.8 Hz), 3.73*,
3.88, 3.66, 4.88, 1.17 (d, 3 H, J5,6 & 6.4 Hz); GalA
8-Methoxycarbonyloctyl 5-N-acetyl-a-neuraminyl-
(2!3)-b-d-galacto-pyranosyl-(1!3)-[a-l-fucopy-
ranosyl-(1!4)]-2-deoxy-2-(methyl b-d-glucopyr-
(from H-1 to H-5, OCH3): ꢃ 4.35 (d, 1 H, J1,2 &
8.0 Hz), 3.59, 3.65, 4.18, 4.16, 3.57; aglycon: ꢃ 2.31,
1.62, 1.31, 1.58, 3.51, 3.81, 3.59; 13C NMR
(CD3OD, 100.61 MHz): GlcN (from C-1 to C-6): ꢃ
102.2, 57.7, 78.0, 77.4, 77.4, 61.4; Gal (from C-1 to
C-6): ꢃ 104.2, 71.0, 77.7, 69.3, 76.8, 63.2; Neu5Ac
(from C-1 to C-9, HNCOCH3): ꢃ 175.0, 101.8,
41.7, 69.6*, 53.9, 74.9, 70.0, 73.0, 64.6, 176.0, 22.6;
Fuc (from C-1 to C-6): 99.6, 70.0*, 71.1, 73.7, 67.6,
16.6; GlcA (from C-1 to C-6, OCH3): ꢃ 105.8, 72.0,
74.5, 71.1, 76.4, 171.6, 58.1; aglycon: ꢃ 175.4, 34.8,
26.0, 30.3, 26.9, 30.6, 70.2, 52.0. MS calcd for
C46H78N2O30: 1138; found [M H]- 1137. Anal.
Calcd for C46H78N2O30: C, 48.50; H, 6.90. Found:
C, 48.31; H, 6.68.
anosyluronamide)-b-d-glucopyranoside
(10a).Ð
According to general procedure D, compound 9a
(20 mg, 20.1 ꢂmol) was incubated with GDP-Fuc
(18.4 mg, 29 ꢂmol) for 1 day to give the title com-
pound (18.8 mg, 82%). 1H NMR (CD3OD,
500.13 MHz): GlcN (from H-1 to H-6a,6b): ꢃ 4.50
(d, 1 H, J1,2 & 7.6 Hz), 4.01, 4.09, 3.77, 3.42, 3.65*,
3.88; Gal (from H-1 to H-6a,6b): ꢃ 4.59 (d, 1 H, J1,2
& 7.4 Hz), 3.52, 3.88, 3.91, 3.54, 3.64*, 3.78;
Neu5Ac (from H-3ax,3eq to H-9a,9b HNCOCH3):
ꢃ 1.91 (t, 1 H, J3ax,4 & 12.1 Hz), 2.80 (dd, 1 H,
J3eq,4 & 4.2, J3ax,3eq & 12.1 Hz), 3.72, 3.74, 3.64,
3.52, 3.83, 3.65, 3.88, 2.03; Fuc (from H-1 to H-6):
ꢃ 5.06 (d, 1 H, J1,2 & 3.8 Hz), 3.74, 3.86, 3.65, 4.85,
1.18 (d, 3 H, J5,6 & 6.4 Hz); GlcA (from H-1 to H-
5, OCH3): ꢃ 4.36 (d, 1 H, J1,2 & 8.0 Hz), 3.28, 3.50,
3.58, 3.68, 3.59; aglycon: ꢃ 2.35, 1.62, 1.32, 1.38,
1.58, 3.47, 3.85, 3.68; 13C NMR (CD3OD,
100.61 MHz): GlcN (from C-1 to C-6): ꢃ 102.4,
56.9, 77.6, 77.3, 77.1, 63.3; Gal (from C-1 to C-6): ꢃ
103.9, 70.9, 77.6, 69.4, 77.4, 61.3; Neu5Ac (from C-
1 to C-9, HNCOCH3): ꢃ 175.2, 102.1, 41.4, 70.0,
54.0, 73.9, 70.9, 72.9, 64.6, 175.5, 22.7; Fuc (from
C-1 to C-6): ꢃ 99.6, 69.6, 71.1, 73.6, 67.6, 16.6;
GlcA (from C-1 to C-6, OCH3): ꢃ 105.4, 74.6, 77.4,
73.5, 74.4, 172.2, 57.8; aglycon: ꢃ 176.1, 34.8, 26.0,
30.2, 26.9, 30.6, 70.7, 52.0. MS Calcd for
C46H78N2O30: 1138; Found [M H]- 1137. Anal.
Calcd for C46H78N2O30: C, 48.50; H, 6.90. Found:
C, 48.15; H, 7.21.
8-Methoxycarbonyloctyl 5-N-acetyl-a-neuraminyl-
(2!3)-b-d-galacto-pyranosyl-(1!3)-[a-l-fucopy-
ranosyl-(1!4)]-2-deoxy-2-(methyl a-d-galactopy-
ranosyluronamide)-b-d-glucopyranoside
(10c).Ð
According to general procedure D, compound 9c
(22.0 mg, 22.2 ꢂmol) was incubated with GDP-Fuc
(21.7 mg, 34.2 ꢂmol) for 1 day to give the title
1
compound (20.1 mg, 79%). H NMR (CD3OD,
400.13 MHz): GlcN (from H-1 to H-6a,6b): ꢃ 4.84
(d, 1 H, J1,2 & 7.6 Hz), 3.71, 3.89, 3.75, 3.42, 3.91;
Gal (from H-1 to H-6a,6b): ꢃ 4.68 (d, 1 H, J1,2
7.4 Hz), 3.52, 3.91*, 3.92*, 3.50, 3.64, 3.75; Neu5Ac
&
(from H-3ax,3eq to H-9a,9b, HNCOCH3): ꢃ 1.88
(t, 1 H, J3ax,4 & 12.1 Hz), 2.79 (dd, 1 H, J3eq,4
&
4.2, J3ax,3eq & 12.1 Hz), 3.74, 3.76, 3.57, 3.50, 3.83,
3.65, 3.88, 2.01; Fuc (from H-1 to H-6): ꢃ 5.06 (d, 1
H, J1,2 & 3.8 Hz), 3.73, 3.86, 3.65, 4.86, 1.17 (d, 3
H, J5,6 & 6.4 Hz); GalA (from H-1 to H-5, OCH3):
ꢃ 4.91 (d, 1 H, J1,2 & 4.9 Hz), 3.92, 3.83, 4.29, 4.25,
3.50; aglycon: ꢃ 2.34, 1.60, 1.32, 1.57, 3.50, 3.83,
3.69; 13C NMR (CD3OD, 100.61 MHz): GlcN
(from C-1 to C-6): ꢃ 101.7, 58.3, 77.4, 77.2, 76.1,
61.4; Gal (from C-1 to C-6): ꢃ 103.9, 71.0, 77.5,
69.9, 77.2, 63.1; Neu5Ac (from C-1 to C-9,
HNCOCH3): ꢃ 175.2, 101.4, 41.4, 69.4*, 53.8, 74.7,
69.9, 72.8, 64.4, 175.6, 22.7; Fuc (from C-1 to C-6):
ꢃ 99.5, 69.5*, 70.9, 73.6, 67.7, 16.6; GalA (from C-1
to C-6, OCH3): 102.1, 69.2, 72.8, 71.2, 72.6, 172.0,
56.6; aglycon: ꢃ 176.4, 34.8, 26.0, 30.1, 30.2, 26.9,
8-Methoxycarbonyloctyl 5-N-acetyl-a-neuraminyl-
(2!3)-b-d-galacto-pyranosyl-(1!3)-[a-l-fucopy-
ranosyl-(1!4)]-2-deoxy-2-(methyl b-d-galactopy-
ranosyluronamide)-b-d-glucopyranoside
(10b).Ð
According to general procedure D, compound 9b
(26 mg, 26.2 ꢂmol) was incubated with GDP-Fuc
(22.6 mg, 35.6 ꢂmol) for one day to give the title
compound (18.8 mg, 63%). A TLC of the crude
mixture still showed some starting sugar. 1H NMR
(CD3OD, 400.13 MHz): GlcN (from H-1 to H-
6a,6b): ꢃ 4.70 (d, 1 H, J1,2 & 7.6 Hz), 3.85, 3.89,