J. Savolainen, R. Leino et al.
(brs, 2H), 4.54 (brs, 1H), 4.28 (ddd, J=11.6, 5.4, 3.8 Hz, 1H), 4.06 (ddd,
J=11.3, 6.8, 4.3 Hz, 1H), 3.89 (dd, J=12.2, 2.3 Hz, 1H), 3.87 (dd, J=
3.1 Hz, 1H), 3.70 (dd, J=12.2, 6.5 Hz, 1H), 3.63 (t, J=6.3 Hz, 2H), 3.56
(dd, J=9.6, 3.1 Hz, 1H), 3.53 (dd, J=9.6, 9.2 Hz, 1H), 3.31 (ddd, J=8.9,
6.5, 2.2 Hz, 1H), 1.86 ppm (quintet, J=6.3 Hz, 1H); 13C NMR
(150.90 MHz, D2O): d=144.6 (triazole-C), 126.3 (triazole-CH), 100.6,
76.9, 73.4, 71.0, 68.4, 67.6, 67.4, 63.4, 61.7, 51.0, 29.3 ppm; ESI-HRMS:
calcd for C25H42N6O14Na [M+Na]+: 673.2657; found: 673.2654.
1,2,3-Tris{1-[(2,3,4,6-tetra-O-acetyl-b-d-mannopyranosyl)-(1!2)-(3,4,6-
tri-O-acetyl-b-d-mannopyranosyloxyethyl)]-4-(methyl-1-oxy)-1,2,3-triazo-
lyl}propane (31): By following general procedure C, the azide–alkyne cy-
cloaddition reaction between azidoethyl glycoside 12 (100 mg,
0.14 mmol) and compound 3 (8.9 mg, 0.04 mmol) in the presence of cop-
per(II) sulfate (2.1 mg, 0.01 mmol) and sodium ascorbate (5.1 mg,
0.03 mmol) gave the title compound 31 (100 mg, 100%, quantitative
yield). Rf =0.45 (CH2Cl2/MeOH, 19:1); [a]2D5 =ꢀ74.18 (c=1, CHCl3);
1H NMR (600.13 MHz, CDCl3): d=7.89 (s, 1H; triazole-H), 7.81 (s, 1H;
triazole-H), 7.78 (s, 1H; triazole-H), 5.52 (dd, J=3.4, 1.0 Hz, 1H), 5.51–
5.50 (m, 2H), 5.23–5.18 (m, 6H), 5.08–5.02 (m, 3H), 4.80 (d, J=3.1 Hz,
2H), 4.76 (d, J=1.0 Hz, 1H), 4.73 (d, J=1.0 Hz, 1H), 4.71 (d, J=1.0 Hz,
1H), 4.68–4.61 (m, 12H), 4.59 (t, J=4.3 Hz, 1H), 4.58 (d, J=0.8 Hz,
1H), 4.57 (d, J=0.8 Hz, 1H), 4.56 (d, J=0.8 Hz, 1H), 4.33–4.28 (m, 6H),
4.25–4.19 (m, 6H), 4.15–4.10 (m, 3H), 4.05–3.96 (m, 6H), 3.84 (quintet,
J=5.0 Hz, 1H), 3.68–3.61 (m, 7H), 3.56–3.52 (m, 3H), 2.23 (brs, 6H),
2.23 (s, 3H), 2.11 (brs, 9H), 2.09 (brs, 6H), 2.08 (s, 3H), 2.04 (brs, 6H),
2.03 (s, 3H), 2.03 (brs, 6H), 2.02 (s, 3H), 2.02 (brs, 9H), 2.00 (brs, 6H),
1.99 ppm (s, 3H); 13C NMR (150.90 MHz, CDCl3): d=170.9 (3C), 170.7
(3C), 170.4 (6C), 169.9 (3C), 169.8 (3C), 169.3 (3C), 145.7 (triazole-C),
145.1 (2C; 2 triazole-C), 123.8 (triazole-CH), 123.7 (2C; 2 triazole-CH),
100.2 (2C), 100.1, 98.1 (2C), 98.0, 77.2, 72.3 (3C), 72.1, 72.0 (4C), 71.9
(4C), 70.9 (3C), 70.2, 70.1, 68.6, 68.5 (2C), 68.3 (3C), 66.2 (3C), 64.9
(3C), 64.6 (2C), 63.7, 62.5 (3C), 61.8 (3C), 50.1 (2C), 50.0, 20.8 (10C),
20.7 ppm (11C); MALDI-TOF-MS: calcd for C96H131N9O57Na [M+Na]+:
2344.752; found: 2344.757.
1,3-Di{1-[(b-d-mannopyranosyl)-(1!2)-(b-d-mannopyranosyloxyethyl)]-
4-(methyl-1-oxy)-1,2,3-triazolyl}propane (28): By following general proce-
dure D, deacetylation of compound 25 (58 mg, 0.04 mmol) with sodium
methoxide (125 mL, 1m in MeOH) gave the title compound 28 (31 mg,
86%). [a]2D5 =ꢀ38.98 (c=1, H2O). Due to the similar structures and
chemical environments of the carbohydrate moieties and the linker parts,
the chemical shifts of the individual saccharide parts along with attached
linker portions in the oligovalent assembly cannot be differentiated and
appear as one. Therefore, the proton integrals in the 1H NMR spectrum
and the carbon signals in the 13C NMR spectrum relate to half of the
molecule. 1H NMR (600.13 MHz, D2O): d=8.11 (s, 1H; triazole-H),
4.70–4.67 (m, 3H), 4.65 (brs, 2H), 4.46 (d, J=1.0 Hz, 1H), 4.34 (dt, J=
11.4, 4.5 Hz, 1H), 4.10–4.06 (m, 2H), 3.90 (td, J=12.1, 2.3 Hz, 2H), 3.84
(dd, J=2.8, 1.1 Hz, 1H), 3.70 (ddd, J=12.0, 6.6, 5.1 Hz, 2H), 3.65 (t, J=
6.4 Hz, 2H), 3.58 (dd, J=9.8, 3.4 Hz, 1H), 3.54–3.49 (m, 3H), 3.35 (ddd,
J=9.6, 6.5, 2.2 Hz, 1H), 3.22 (ddd, J=9.2, 4.3, 2.2 Hz, 1H), 1.89 ppm
(quintet, J=6.4 Hz, 1H); 13C NMR (150.90 MHz, D2O): d=144.9 (tria-
zole-C), 125.5 (triazole-CH), 101.1, 100.9, 78.0, 77.0, 76.9, 73.4, 72.7, 70.9,
68.2, 67.7 (2C), 67.4, 63.4, 61.7, 61.5, 51.0, 29.3 ppm; ESI-HRMS: calcd
for C37H62N6O24Na [M+Na]+: 997.3713; found: 997.3703.
1,2,3-Tris{1-[(2,3,4,6-tetra-O-acetyl-b-d-mannopyranosyl)-(1!2)-(3,4,6-
tri-O-acetyl-a-d-mannopyranosyloxyethyl)]-4-(methyl-1-oxy)-1,2,3-triazo-
lyl}propane (32): The title compound was synthesized according to gener-
al procedure C. Rf =0.45 (CH2Cl2/MeOH, 13:1); [a]2D5 =ꢀ67.58 (c=1,
1,3-Di{1-[(b-d-mannopyranosyl)-(1!2)-(a-d-mannopyranosyloxyethyl)]-
4-(methyl-1-oxy)-1,2,3-triazolyl}propane (29): By following general proce-
dure D, deacetylation of compound 26 (40 mg, 0.03 mmol) with sodium
methoxide (85 mL, 1m in MeOH) gave the title compound 29 (17 mg,
68%). [a]2D5 =ꢀ2.48 (c=1, H2O). Due to the similar structures and chemi-
cal environments of the carbohydrate moieties and the linker parts, the
chemical shifts of the individual saccharide parts along with attached
linker portions in the oligovalent assembly cannot be differentiated and
appear as one. Therefore, the proton integrals in the 1H NMR spectrum
and the carbon signals in the 13C NMR spectrum relate to half of the
molecule. 1H NMR (600.13 MHz, D2O): d=8.09 (s, 1H; triazole-H), 4.90
(d, J=1.7 Hz, 1H), 4.70–4.67 (m, 3H), 4.63 (brs, 2H), 4.11 (ddd, J=11.2,
7.3, 4.0 Hz, 1H), 4.07 (dd, J=3.0, 1.7 Hz, 1H), 4.00 (dd, J=3.2, 0.9 Hz,
1H), 3.94 (ddd, J=11.0, 5.3, 3.7 Hz, 1H), 3.90 (dd, J=12.3, 2.3 Hz, 1H),
3.74–3.61 (m, 8H), 3.56 (t, J=9.7 Hz, 1H), 3.35 (ddd, J=9.8, 6.6, 2.3 Hz,
1H), 3.01 (ddd, J=9.0, 4.9, 2.5 Hz, 1H), 1.89 ppm (quintet, J=6.3 Hz,
1H); 13C NMR (150.90 MHz, D2O): d=144.8 (triazole-C), 126.2 (tria-
zole-CH), 99.2, 98.0, 77.7, 77.0, 73.5, 73.4, 71.4, 70.4, 67.6, 67.3, 67.2, 66.2,
63.4, 61.6, 60.9, 50.7, 29.3 ppm; ESI-HRMS: calcd for C37H62N6O24Na
[M+Na]+: 997.3713; found: 997.3754.
1
CHCl3); H NMR (600.13 MHz, CDCl3): d=7.80 (s, 1H; triazole-H), 7.73
(s, 1H; triazole-H), 7.72 (s, 1H; triazole-H), 5.48–5.46 (m, 3H), 5.25–5.21
(m, 6H), 5.04–5.00 (m, 3H), 4.91–4.87 (m, 3H), 4.81–4.77 (m, 5H), 4.70–
4.69 (m, 3H), 4.67–4.55 (m, 10H), 4.34–4.30 (m, 3H), 4.28–4.27 (m, 3H),
4.20–4.16 (m, 3H), 4.14–4.09 (m, 3H), 4.02–3.99 (m, 6H), 3.93–3.90 (m,
3H), 3.82 (quintet, J=5.2 Hz, 1H), 3.69–3.54 (m, 10H), 2.23 (brs, 9H),
2.12 (brs, 9H), 2.09 (brs, 9H), 2.04 (brs, 9H), 2.03 (brs, 6H), 2.02 (brs,
9H), 2.01 (s, 3H), 2.00 ppm (brs, 9H); 13C NMR (150.90 MHz, CDCl3):
d=170.8 (3C), 170.6, 170.5 (2C), 170.3, 170.2 (4C), 170.1, 169.9, 169.8
(2C), 169.6 (3C), 169.2, 169.1 (2C), 145.5 (triazole-C), 145.0 (triazole-C),
144.9 (triazole-C), 123.8 (triazole-CH), 123.7 (2C; 2 triazole-CH), 97.4
(3C), 96.2 (3C), 77.1, 72.1 (2C), 72.0, 71.9, 71.8 (2C), 70.6, 70.5 (2C),
70.0 (4C), 69.9, 68.9 (2C), 68.8, 68.4 (3C), 66.0 (3C), 65.9 (3C), 64.7
(3C), 64.4 (2C), 63.5, 62.3 (3C), 61.6, 61.5 (2C), 49.7 (2C), 49.6, 20.7
(6C), 20.6 (6C), 20.5 (6C), 20.4 ppm (3C); MALDI-TOF-MS: calcd for
C96H131N9O57Na [M+Na]+: 2344.752; found: 2344.732.
1,2,3-Tris[1-(b-d-mannopyranosyloxyethyl)-4-(methyl-1-oxy)-1,2,3-triazo-
lyl]propane (33): By following general procedure D, deacetylation of
compound 30 (70 mg, 0.05 mmol) with sodium methoxide (150 mL, 1m in
MeOH) gave the title compound 33 (41.8 mg, 91%). [a]2D5 =ꢀ21.58 (c=1,
H2O); 1H NMR (600.13 MHz, D2O): d=8.09 (brs, 2H; 2 triazole-H),
8.08 (s, 1H; triazole-H), 4.73 (s, 2H), 4.72–4.65 (m, 6H), 4.64 (brs, 4H),
4.55 (brs, 2H), 4.54 (s, 1H), 4.31–4.25 (m, 3H), 4.09–4.02 (m, 3H), 3.93–
3.86 (m, 7H), 3.72–3.68 (m, 5H), 3.64–3.50 (m, 8H), 3.34–3.30 ppm (m,
3H); 13C NMR (150.90 MHz, D2O): d=144.1 (triazole-C), 143.8 (2C; 2
triazole-C), 125.7 (3C; 3 triazole-CH), 99.9 (3C), 76.6, 76.2 (3C), 72.7
(3C), 70.3 (3C), 68.9, 67.7 (3C), 66.7 (3C), 63.3 (3C), 62.1, 60.9 (3C),
50.3 ppm (3C); ESI-HRMS: calcd for C36H59N9O21Na [M+Na]+:
976.3724; found: 976.3728.
1,2,3-Tris[1-(2,3,4,6-tetra-O-acetyl-b-d-mannopyranosyloxyethyl)-4-
(methyl-1-oxy)-1,2,3-triazolyl]propane (30): By following general proce-
dure C, the azide–alkyne cycloaddition reaction between azidoethyl gly-
coside 8 (180 mg, 0.43 mmol) and compound 3[21] (27 mg, 0.13 mmol) in
the presence of copper(II) sulfate (6.3 mg, 0.04 mmol) and sodium ascor-
bate (15.5 mg, 0.08 mmol) gave the title compound 30 (170 mg, 89%).
Rf =0.35 (CH2Cl2/MeOH, 19:1); [a]2D5 =ꢀ22.58 (c=1, CHCl3); 1H NMR
(600.13 MHz, CDCl3): d=7.73 (s, 1H; triazole-H), 7.68 (s, 1H; triazole-
H), 7.67 (s, 1H; triazole-H), 5.44 (dd, J=2.2, 1.1 Hz, 3H), 5.24 (td, J=
10.0, 2.6 Hz, 3H), 5.07–5.03 (m, 3H), 4.79–4.70 (m, 5H), 4.66–4.57 (m,
7H), 4.53–4.46 (m, 3H), 4.30–4.21 (m, 6H), 4.15 (dd, J=12.2, 2.4 Hz,
3H), 3.96–3.90 (m, 3H), 3.81 (quintet, J=5.2 Hz, 1H), 3.71–3.58 (m,
7H), 2.18 (brs, 6H), 2.17 (s, 3H), 2.09 (brs, 9H), 2.04 (brs, 9H), 1.99 (s,
3H), 1.98 ppm (brs, 6H); 13C NMR (150.90 MHz, CDCl3): d=170.6
(3C), 170.2 (2C), 170.1, 169.8 (3C), 169.5 (3C), 145.4 (triazole-C), 144.9
(2C; 2 triazole-C), 124.1 (triazole-CH), 124.0 (triazole-CH), 123.9 (tria-
zole-CH), 98.7 (2C), 98.6, 77.1, 72.4 (3C), 70.7, 70.6 (2C), 70.0 (2C), 68.5
(3C), 68.3, 68.2 (2C), 65.9 (3C), 64.6 (2C), 63.7, 62.3 (3C), 49.8 (2C),
49.7, 20.8 (3C), 20.7 (3C), 20.6 (3C), 20.5 ppm (3C); ESI-HRMS: calcd
for C60H83N9O33Na [M+Na]+: 1480.4991; found: 1480.4989.
1,2,3-Tris{[1-(b-d-mannopyranosyl)-(1!2)-(b-d-mannopyranosyloxyeth-
yl)]-4-(methyl-1-oxy)-1,2,3-triazolyl}propane (34): By following general
procedure D, deacetylation of compound 31 (60.7 mg, 0.03 mmol) with
sodium methoxide (130 mL, 1m in MeOH) gave the title compound 34
(32.9 mg, 87%). [a]2D5 =ꢀ36.88 (c=1, H2O); 1H NMR (600.13 MHz,
D2O): d=8.12 (brs, 3H; 3 triazole-H), 4.77 (brs, 3H), 4.70–4.66 (m,
12H), 4.46–4.45 (m, 3H), 4.35–4.31 (m, 3H), 4.11–4.05 (m, 6H), 3.92–
3.86 (m, 7H), 3.84–3.82 (m, 3H), 3.74–3.67 (m, 8H), 3.66–3.63 (m, 2H),
3.58 (t, J=3.1 Hz, 1H), 3.57 (2t, J=3.1 Hz, 2H), 3.54–3.48 (m, 9H),
&
10
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ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
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