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24b as a white foam; yield: 140 mg (91%); [a]2D2: +5.58 (c 1,
CHCl3). H NMR (500 MHz, CDCl3): d=7.64 (s, 1H), 5.27
76.3, 73.5, 71.0, 70.8, 70.1, 69.2, 69.2, 69.0, 69.0, 67.9, 66.8,
66.3, 65.8, 64.7, 62.3, 62.1, 60.8, 50.8, 49.7, 44.9, 24.3, 20.9,
20.9, 20.8, 20.8, 20.8, 20.8, 20.7, 20.7, 20.6; HR-MS (ESI+):
m/z=2245.6907, calcd. for C90H125N9O53S2 [M+H]+:
2245.6876; IR (neat): n=1747, 1369, 1224, 1139, 1047 cmꢁ1.
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(dd, J=3.5, 1.2 Hz, 1H), 5.13 (m, 4H), 5.02 (dd, J=10.4,
7.9 Hz, 1H), 4.90 (dd, J=10.4, 3.5 Hz, 1H), 4.85 (t, J=
9.7 Hz, 1H), 4.72 (s, 1H), 4.61 (s, 2H), 4.53 (m, 3H), 4.45
(m, 2H), 4.28 (m, 2H), 4.12 (dd, J=12.3, 5.2 Hz, 1H), 4.04
(m, 3H), 3.96 (m, 2H), 3.83 (m, 2H), 3.68 (m, 3H), 3.62–
3.56 (m, 13H), 3.49 (m, 2H), 3.41 (ddd, J=14.4, 11.4,
4.8 Hz, 1H), 3.06 (ddd, J=14.2, 11.5, 4.8 Hz, 1H), 2.91 (m,
1H), 2.07 (s, 3H), 2.06 (s, 3H), 2.06 (s, 3H), 2.01 (s, 3H),
1.98 (s, 3H), 1.96 (m, 12H), 1.91 (s, 3H), 1.88 (s, 3H);
13C NMR (126 MHz, CDCl3): d=170.4, 170.4, 170.2, 170.0,
169.9, 169.8, 169.8, 169.5, 169.5, 169.0, 145.1, 123.9, 101.0,
97.4, 83.7, 76.9, 76.1, 73.4, 70.9, 70.7, 70.6, 70.5, 70.4, 70.4,
69.9, 69.6, 69.5, 69.1, 69.0, 68.9, 68.9, 68.8, 66.6, 66.2, 65.6,
64.3, 62.1, 61.9, 60.8, 51.4, 49.6, 24.1, 20.7, 20.7, 20.6, 20.6,
20.5, 20.4; HR-MS (ESI+): m/z=1392.4211, calcd. for
C55H82N3O34S2 [M+H]+: 1392.4221; IR (neat): n=1744,
1433, 1368, 1218 cmꢁ1.
Compound 26: Under argon, to a solution of 3g (70.0 mg,
0.20 mmol), 4j (168 mg, 0.26 mmol) in degassed CH2Cl2/2-
propanol (12 mL, 5:1), PPh3 (16.3 mg, 0.06 mmol) and a cata-
lytic amount of Et3N were added and the mixture was
stirred at room temperature for 24 h under an inert atmos-
phere. The solvent was removed under reduced pressure
and the residue purified by column chromatography (SiO2,
CH2Cl2/EtOAc 9:1 to 7:3) to give 26 as a syrup; yield:
187 mg (91%); [a]D22: ꢁ2.58 (c 1, CHCl3). 1H NMR
(400 MHz, CDCl3): d=5.33 (d, J=3.4 Hz, 1H), 5.20 (t, J=
9.1 Hz, 1H), 5.09 (dd, J=10.5, 7.8 Hz, 1H), 4.94 (m, 2H),
4.50 (m, 3H), 4.21 (m, 2H), 4.12–4.01 (m, 9H), 3.87 (t, J=
6.8 Hz, 1H), 3.74 (t, J=9.4 Hz, 1H), 3.64 (m, 1H), 3.53–3.48
(m, 7H), 3.40 (m, 1H), 3.11 (ddd, J=16.2, 11.5, 4.8 Hz, 1H),
2.96 (ddd, J=14.1, 11.5, 4.9 Hz, 1H), 2.45 (s, 3H), 2.13 (s,
6H), 2.05 (s, 3H), 2.03 (m, 9H), 1.94 (s, 3H); 13C NMR
(126 MHz, CDCl3): d=170.6, 170.4, 170.2, 170.1, 169.7,
169.6, 169.2, 101.2, 84.2, 79.6, 76.2, 74.9, 74.9, 73.5, 71.1, 70.9,
70.0, 69.5, 69.2, 68.2, 66.7, 62.1, 60.9, 58.8, 51.0, 44.5, 24.4,
20.9, 20.8, 20.8, 20.7, 20.6. HR-MS (ESI+): m/z=1015.2520,
calcd. for C42H56O23S2Na [M+Na]+: 1015.2551; IR (neat):
n=1742, 1366, 1213, 1166, 1083, 1042 cmꢁ1.
Compound 27: A solution of 26 (103 mg, 0.10 mmol) and
23b (174 mg, 0.42 mmol) in anhydrous THF (6 mL) was de-
gassed by flowing argon. (EtO)3P·CuI (37.0 mg, 0.10 mmol)
and DIPEA (220 mL, 1.25 mmol) were added and the mix-
ture was stirred for 4 d under an argon atmosphere. The sol-
vent was removed under reduced pressure and the crude pu-
rified by column chromatography (SiO2, CH2Cl2/MeOH
98:2 to 95:5) to give 27 as a colourless syrup; yield: 200 mg
(86%); [a]2D2: +8.88 (c 1, CHCl3). 1H NMR (500 MHz,
CDCl3): d=7.71 (s, 3H), 5.33 (d, J=3.4 Hz, 1H), 5.24–5.18
(m, 10H), 5.06 (dd, J=10.4, 7.9 Hz, 1H), 4.96 (dd, J=10.4,
3.4 Hz, 1H), 4.89 (t, J=9.7 Hz, 1H), 4.79 (d, J=1.4 Hz,
3H), 4.67–4.56 (m, 13H), 4.51 (m, 2H), 4.18 (m, 5H), 4.10
(m, 5H), 4.02 (m, 4H), 3.89 (ddd, J=10.8, 6.3, 4.2 Hz, 4H),
3.75 (t, J=9.4 Hz, 1H), 3.68 (ddd, J=10.2, 6.0, 2.1 Hz, 1H),
3.62 (m, 3H), 3.46–3.40 (m, 8H), 3.05 (ddd, J=15.7, 10.6,
5.4 Hz, 1H), 2.89 (ddd, J=14.0, 10.7, 5.6 Hz, 1H), 2.12 (s,
3H), 2.11 (m, 9H), 2.08 (s, 3H), 2.07 (m, 9H), 2.03 (s, 3H),
2.01 (m, 18H), 1.96 (s, 9H), 1.93 (s, 3H); 13C NMR
(126 MHz, CDCl3): d=170.6, 170.5, 170.4, 170.2, 170.1,
170.0, 169.7, 169.7, 169.2, 145.1, 124.0, 101.2, 97.6, 83.7, 76.9,
General Procedure for O-Acetyl Deprotection
A solution of 17a–d, 24a, b or 27 (0.06–0.08 mmol) and Et3N
(0.8 mL) in anhydrous MeOH (8 mL) was stirred for 24–
120 h at room temperature. The mixture was concentrated
under reduced pressure and the residue purified by column
chromatography (SiO2, CH3CN/H2O 4:1 to 3:1). The prod-
uct-containing fractions were combined and the volatiles re-
moved under reduced pressure. The resulting solution was
freeze-dried to yield the corresponding deprotected homo-
and heterogeneous divalent glycosylated systems 18a–d, 25a,
b or 28.
Compound 18a: Obtained from 17a (86.0 mg, 0.078 mmol)
as a white foam after stirring for 24 h; yield: 56.0 mg (94%);
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[a]2D2: ꢁ22.48 (c 1, MeOH). H NMR (500 MHz, D2O): d=
4.65 (d, J=9.9 Hz, 2H), 4.52 (m, 4H), 3.93 (d, J=12.4 Hz,
2H), 3.89 (m, 4H), 3.82–3.71 (m, 14H), 3.52 (m, 4H), 3.44
(t, J=9.3 Hz, 2H), 3.37 (t, J=9.4 Hz, 2H), 3.26 (ddd, J=
15.3, 9.1, 6.1 Hz, 2H), 3.17 (ddd, J=14.7, 9.1, 6.4 Hz, 2H);
13C NMR (126 MHz, D2O): d=85.6, 79.9, 77.1, 72.1, 70.4,
69.8, 69.6, 69.4, 68.4, 60.8, 50.5, 23.4; HR-MS (ESI+): m/z=
767.1573, calcd. for C24H47O19S4 [M+H]+: 767.1594;
784.1843, calc. for C24H50NO19S4 [M+NH4]+: 748.1860; IR
(neat): n=3380, 2880, 1349, 1166, 1041 cmꢁ1.
Compound 18b: Synthesized from 17b (90.0 mg,
0.082 mmol) as a white solid after stirring for 24 h; yield:
48.0 mg (77%); [a]D22: +1328 (c 1, MeOH). 1H NMR
(400 MHz, D2O): d=5.44 (d, J=1.5 Hz, 2H), 4.53 (m, 4H),
4.11 (dd, J=3.3, 1.5 Hz, 2H), 4.03 (ddd, J=9.2, 6.4, 2.2 Hz,
2H), 3.94 (dd, J=12.3, 2.3 Hz, 2H), 3.90 (m, 4H), 3.85–3.75
(m, 16H), 3.71 (t, J=9.7 Hz, 2H), 3.17 (m, 4H); 13C NMR
(101 MHz, D2O): d=85.2, 73.3, 71.4, 71.0, 70.4, 69.8, 69.6,
68.4, 67.0, 60.8, 49.7, 24.2; HR-MS (ESI+): m/z=767.1607,
calcd. for C24H47O19S4 [M+H]+: 767.1594; 784.1879, calc. for
C24H50NO19S4 [M+NH4]+: 748.1860; IR (neat): n=3366,
2928, 1350, 1166, 1072 cmꢁ1.
Compound 18c: Obtained from 17c (98.0 mg, 0.058 mmol)
as a white solid after stirring for 5 d; yield: 41.0 mg (65%);
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[a]22: ꢁ6.08 (c 1, H2O). H NMR (400 MHz, D2O): d=4.70
(d,DJ=9.9 Hz, 2H), 4.54 (m, 4H), 4.50 (d, J=7.8 Hz, 2H),
4.02 (dd, J=12.4, 2.1 Hz, 2H), 3.97 (d, J=3.4 Hz, 2H), 3.91
(m, 4H), 3.86–3.76 (m, 20H), 3.73–3.65 (m, 8H), 3.59 (dd,
J=10.0, 7.8 Hz, 2H), 3.45 (m, 2H), 3.24 (m, 4H); 13C NMR
(101 MHz, D2O): d=102.8, 85.4, 78.7, 78.1, 75.7, 75.3, 72.5,
71.8, 70.9, 70.4, 69.8, 69.6, 68.5, 68.4, 61.0, 60.1, 50.4, 23.4;
HR-MS (ESI+): m/z=1091.2650, calcd. for C36H67O29S4 [M+
H]+: 1091.2651; 1108.2909, calc. for C36H70NO29S4 [M+
NH4]+: 1108.2916; IR (neat): n=3356, 2881, 1639, 1347,
1072 cmꢁ1.
Compound 18d: Obtained from 17d (146 mg, 0.077 mmol)
as a colourless syrup after stirring for 24 h; yield: 96 mg
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(80%); [a]22: +54.78 (c 1, H2O); H NMR (400 MHz, D2O):
d=5.43 (s,D2H), 4.53 (t, J=4.1 Hz, 4H), 4.10 (m, 2H), 4.02
(t, J=7.8, 2H), 3.94 (d, J=12.5 Hz, 2H), 3.89 (m, 4H), 3.74
(m, 114H), 3.15 (m, 4H); 13C NMR (101 MHz, D2O): d=
85.3, 73.3, 71.4, 71.0, 70.3, 69.7, 69.5, 68.4, 67.0, 60.8, 49.7,
Adv. Synth. Catal. 0000, 000, 0 – 0
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