J. Tejler et al. / Carbohydrate Research 341 (2006) 1353–1362
1361
and CuI (21 mg, 0.11 mmol) were dissolved in toluene
(3 mL). N,N-Diisopropylethylamine (15 lL, 81 lmol)
was added and the reaction mixture was stirred for 2 days
followed by concentration under reduced pressure. Puri-
fication by flash chromatography (4:1, CH2Cl2/CH3OH)
3.11 (dd, 1H, J = 8.2 Hz, J = 14.0 Hz, –NH–CH–CO,
partly hidden), 3.11 (dd, 1H, J = 8.3 Hz, J = 13.7 Hz,
–NH–CH–CO); ESIMS m/z calcd for [C48H70N8O28+
H]+: 1207.4378. Found: 1207.4337.
1
gave 14 (31 mg, 60%). H NMR (300 MHz, CH3OD): d
4.16. Trivalent lactosyl methylester carbamate (17)
8.47 (s, 1H, H-triazole), 7.30–7.20 (m, 5H, Ar–H), 4.69
(t, 2H, J = 4.8 Hz, –CH2–CH2–N), 4.60 (m, 1H, NH),
4.35 (br d, 2H, J = 7.2 Hz, H-1, H-10), 4.27–4.20 (m,
1H, O–CH2–CH2), 4.06–4.99 (m, 1H, O–CH2–CH2),
3.90–3.66 (m, 8H), 3.60–3.45 (m, 5H), 3.43–3.37 (m, 1H,
H-5), 3.28–3.21 (m, 3H, H-2, Ar–CH2), 3.19–3.12 (m,
1H, NH–CH–CO); ESIMS m/z calcd for [C27H38-
N4O14+ Na]+: 665.2282. Found: 665.2265.
2-Azidoethyl b-D-galactopyranosyl-(1!4)-b-D-gluco-
pyranoside 1132 (62 mg, 0.15 mmol), 10 (21 mg, 39 lmol)
and CuI (30 mg, 0.15 mmol) were dissolved in CH3CN
(3 mL). N,N-Diisopropylethylamine (26 lL, 150 lmol)
was added and the reaction mixture was stirred over
2 days followed by concentration under reduced pressure.
The residue was dissolved in H2O and applied on to C-18
silica (5 g). Elution with a gradient of CH3OH in H2O and
lyophilization gave 17 (23 mg, 33%): 1H NMR (400 MHz,
D2O): d 8.46–8.44 (m, 3H, triazole), 7.09–7.01 (m, 3H,
Ar–H), 4.77–4.73 (m, 6H, –CH2–CH2–N, partly hidden
in solvent residual peak), 4.47–4.43 (m, 6H, H-1, H-10),
4.32–4.29 (m, 3H, O–CH2–CH2), 4.16–4.13 (m, 3H,
O–CH2–CH2), 3.94–3.90 (m, 6H), 3.83–3.53 (m, 39H),
3.32–3.08 (m, 9H, H-2, Ar–CHa, NH–CH–CO); ESIMS
m/z calcd for [C69H102N12O42+Na]+: 1793.6112. Found:
1793.6088.
4.14. Lactosyl methylester amide (15)
2-Azidoethyl b-D-galactopyranosyl-(1!4)-b-D-gluco-
pyranoside 1132 (30 mg, 73 lmol), 3 (24 mg, 0.11 mmol)
and CuI (34 mg, 0.18 mmol) were dissolved in CH3CN
(2 mL). N,N-Diisopropylethylamine (14 lL, 77 lmol)
was added and the reaction mixture was stirred over
3 days followed by concentration under reduced pressure.
Purification by flash chromatography (4:1, CH2Cl2/
20
CH3OH) gave 15 (28 mg, 60%): ½aꢁ ꢀ31; 1H NMR
D
(400 MHz, CH3OD): d 8.47 (s, 1H, H-triazole), 7.29–
7.18 (m, 5H, Ar–H), 4.68 (t, 2H, J = 5 Hz,
–CH2–CH2–N), 4.59 (br s, 0.5H, N–H, partly
exchanged), 4.35 (d, 1H, J = 7.4 Hz, H-10), 4.35 (d, 1H,
J = 7.8 Hz, H-1), 4.25–4.20 (m, 1H, O–CH2–CH2),
4.05–4.00 (m, 1H, O–CH2–CH2), 3.89 (dd, 1H, J =
2.4 Hz, J = 12.2 Hz, H-6), 3.83–3.67 (m, 7H), 3.59–3.46
(m, 5H), 3.43–3.40 (m, 1H, H-5), 3.30–3.21 (m, 3H, H-2,
Ar–CH2), 3.16 (dd, 1H, J = 8.5 Hz, J = 13.9 Hz, NH–
CH–CO); ESIMS m/z calcd for [C27H38N4O14+H]+:
643.2463. Found: 643.2435.
4.17. Lactosyl methylester carbamate (18)
2-Azidoethyl b-D-galactopyranosyl-(1!4)-b-D-gluco-
pyranoside 1132 (29 mg, 71 lmol), 5 (39 mg, 0.11mmol)
and CuI (14 mg, 0.073 mmol) were dissolved in CH3CN
(2 mL). N,N-Diisopropylethylamine (14 lL, 77 lmol)
was added and the reaction mixture was stirred over
2 days followed by concentration under reduced pressure.
Purification by flash chromatography (4:1, CH2Cl2/
1
CH3OH) gave 18 (27 mg, 56%): H NMR (400 MHz,
CH3OD): d 8.06, 8.05 (2s, 1H, triazole-H, from the two
diastereomers), 7.28–7.17 (m, 5H, Ar–H), 5.09 (s, 2H,
O–CH2–C), 4.63 (t, 2H, J = 5 Hz, –CH2–CH2–N), 4.60
(br s, 0.3H, NH, partly exchanged), 4.43 (dd, 1H, J =
5.6 Hz, J = 9.0 Hz, CH–CO), 4.35 (d, 1H, J = 7.5 Hz,
H-10), 4.34 (d, 1H, J = 7.9 Hz, H-1), 4.25–4.19 (m, 1H, O–
CH2–CH2), 4.03–3.97 (m, 1H, O–CH2–CH2), 3.90 (dd,
1H, J = 2.3 Hz, J = 12.1 Hz, H-6), 3.84–3.75 (m, 3H),
3.72–3.68 (m, 4H), 3.62–3.48 (m, 5H), 3.44–3.40 (m, 1H,
H-5), 3.25 (t, 1H, J = 8.2 Hz, J = 8.3 Hz, H-2), 3.12 (dd,
1H, J = 5.5 Hz, J = 13.8 Hz, Ar–CHa), 2.92 (dd, 1H,
J = 9.1 Hz, J = 13.8 Hz, Ar–CHb); ESIMS m/z calcd
for [C28H40N4O15+H]+: 673.2568. Found: 673.2535.
4.15. Divalent lactosyl methylester amide (16)
2-Azidoethyl b-D-galactopyranosyl-(1!4)-b-D-glucopyr-
anoside 1132 (46 mg, 0.11 mmol), 7 (15 mg, 40 lmol)
and CuI (26 mg, 0.14 mmol) were dissolved in CH3CN
(2 mL). N,N-Diisopropylethylamine (20 lL, 116 lmol)
was added and the reaction mixture was stirred over
6 days followed by concentration under reduced pres-
sure. The residue was dissolved in H2O and applied on
to C-18 silica (5 g). Elution with a gradient of CH3OH
1
in H2O and lyophilization gave 16 (26 mg, 53%): H
NMR (400 MHz, CH3OD): d 8.48 (2s, 1H, triazole-H,
from the diastereomers), 7.21–7.09 (m, 4H, Ar–H),
4.69 (t, 4H, J = 4.9 Hz, –CH2–CH2–N), 4.59 (s, 0.7H,
NH), 4.36 (br d, 4H, J = 7.6 Hz, H-10, H-1), 4.26–4.20
(m, 2H, O–CH2–CH2), 4.06–4.01 (m, 2H, O–CH2–
CH2), 3.89 (br dd, 2H), 3.84–3.67 (m, 14H), 3.61–3.47
(m, 10H), 3.43–3.40 (m, 2H, H-5), 3.33–3.18 (m, 6H,
H-2, Ar–CHa, partly hidden in solvent residual peak),
4.18. Divalent lactosyl methylester carbamate (19)
2-Azidoethyl b-D-galactopyranosyl-(1!4)-b-D-gluco-
pyranoside 1132 (74 mg, 0.18 mmol), 8 (28 mg, 64 lmol)
and CuI (38 mg, 0.20 mmol) were dissolved in CH3CN
(2 mL). N,N-Diisopropylethylamine (31 lL, 178 lmol)
was added and the reaction mixture was stirred over