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L. Zhang et al. / Carbohydrate Research 344 (2009) 2083–2087
1.5. 11-Thioacetylundecyl 2,4,6-tri-O-benzoyl-3-O-propargyl-b-
(400 MHz, CDCl3): d 1.05–1.52 (m, 26H), 1.85, 1.95 1.99, 2.01,
2.29 (5s, 15H), 2.10 (t, 4H, J 5.3 Hz), 2.55 (dd, 1H, J 12.8, 4.8 Hz),
2.83 (t, 2H, J 7.3 Hz), 3.22–3.24 (m, 1H), 3.45–3.47 (m, 1H), 3.75
(s, 3H), 3.88 (t, 1H, J 3.8 Hz), 4.07–4.10 (m, 7H), 4.33 (dd, 1H, J
12.8, 1.8 Hz), 4.60–4.63 (m, 2H), 4.81–4.83 (m, 2H), 5.29 (dd, 1H,
J 10.7, 2.1 Hz), 5.35 (br d, 1H, J 5.8 Hz), 5.43–5.45 (m, 2H), 5.84
(br d, 1H, J 8.6 Hz), 7.41–8.13 (m, 16H); 13C NMR (100 MHz, CDCl3):
d 21.3, 21.4, 21.5, 21.6, 23.6, 23.7, 25.6, 25.7, 26.3, 29.4, 29.6, 29.7,
29.9, 30, 31.2, 38.1, 38.6, 49.8, 49.9, 53.1, 53.2, 62.8, 62.9, 63, 63.1,
62.2, 65.2, 67.9, 69, 69.4, 69.5, 69.7, 70.9 72.3, 72.6, 77.3, 77.7, 78,
99.1, 102.1, 129, 129.1, 130.2, 130.4, 130.6, 133.7, 133.8, 134,
165.7, 166.4, 166.6, 168.2, 170.6, 170.7, 171.1, 171.2, 171.3,
196.6. Anal. Calcd for C69H90N4O23S: C, 60.25; H, 6.59. Found: C,
60.39; H, 6.67. MALDI-TOFMS: calcd for C69H90N4O23S: 1374.57
[M]+; found: 1397.46 [M+Na]+.
D-galactopyranoside (8)
To a mixture of 7 (290 mg, 0.438 mmol), 11-thioacetylundeca-
nol (90.14 mg, 0.366 mmol), and 4 Å molecular sieves (100 mg)
in anhyd CH2Cl2 (5 mL) was added TMSOTf (7.94 L, 0.044 mmol)
l
at 0 °C under an N2 atmosphere. The reaction mixture was stirred
under these conditions for 1.5 h, then neutralized with Et3N and fil-
tered. The filtrate mixture was concentrated to dryness. The resi-
due was purified by silica gel column chromatography (1:3
EtOAc–petroleum ether) to give 8 (594 mg, 95%) as an amorphous
solid: ½a 2D5
ꢁ
+ 127 (c 1, CHCl3); 1H NMR (400 MHz, CDCl3): d 1.08–
1.19 (m, 18H, 9 CH2), 2.32 (s, 3H, OAc), 2.33 (t, 1H, J 2.4 Hz,
„CH), 2.85 (t, 2H, J 7.2 Hz, CH2S), 3.49–3.53 (m, 1H, OCH2), 3.92–
3.96 (m, 1H, OCH2), 4.15–4.20 (m, 3H, H-3, H-5, and one proton
of OCH2C„CH), 4.29 (dd, 1H, J 16.6, 2.4 Hz, another proton of
OCH2C„CH), 4.41 (dd, 1H, J 11.3, 6.3 Hz, H-6a), 4.63 (dd, 1H, J
11.3, 6.7 Hz, H-6b), 4.70 (d, J 8.0 Hz, H-1), 5.48 (dd, 1H, J 10.0,
8.0 Hz, H-2), 5.84 (d, J 3.1 Hz, H-4), 8.00–8.15 (m, 15H, 3Ph). Anal.
Calcd for C43H50O10S: C, 68.05; H, 6.64. Found: C, 67.81; H, 6.59.
MALDI-TOFMS: calcd for C43H50O10S: 758.31 [M]+; found: 781.27
[M+Na]+.
1.8. 11,110-Dithiobis{undecyl [3-O-[(5-acetamido-3,5-dideoxy-
2-O-
a-
D-glycero-
D-galacto-2-nonulopyranosylhexanyl)triazol-1-
methyl]-b-
D-galactopyranoside]} (1)
To a solution of 11 (100 mg, 0.07 mmol) in anhyd MeOH
(20 mL) was added 1 N NaOMe until pH 9.5. The reaction mixture
was stirred at rt for 40 h, then a gentle stream of oxygen was bub-
bled through the solution, and stirring was continued for approxi-
mately 24 h, at the end of which time H2O (3 mL) was added. After
stirring for another 12 h, the reaction mixture was cooled to 0 °C,
neutralized with amberlite IR-120 (H+), and then filtered, and the
filtrate was evaporated. The residue was purified with Sephadex
LH-20 and the desired fractions were lyophilized to give 1
1.6. Methyl (6-azidohexyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,
5-dideoxy-2-O-a-D-glycero-D-galacto-2-nonulopyranosid)uro-
nate (10)
To a stirred mixture of 9 (250 mg, 0.4284 mmol), 6-azido-1-
hexanol (55.7 mg, 0.43 mmol), and 4Å molecular sieves (30 mg)
in dry 1:1 CH2Cl2–CH3CN (5 mL) were added NIS (131 mg,
(48.7 mg, 80%) as a white amorphous solid: ½a D25
ꢁ
+ 90 (c 0.5,
0.64 mmol) and TMSOTf (7
l
L, 0.043 mmol) at ꢀ40 °C. The reaction
H2O); 1H NMR (400 MHz, 49:1 DMSO-d6–D2O): d 1.11–1.46 (m,
26H), 1.72–1.74 (m, 2H), 1.84 (d, 3H, J 7.0 Hz), 2.59 (dd, 1H, J
10.8, 1.8 Hz), 2.61 (t, 2H, J 7.1 Hz), 3.14–3.25 (m, 3H), 3.30–3.38
(m, 3H), 3.46–3.74 (m, 5H), 3.86 (br s, 1H), 4.06 (d, 1H, J 7.7 Hz),
4.25–4.27 (m, 2H), 4.53 (dd, 1H, J 12.2, 2.1 Hz), 4.64 (d, 1H, J
12.2 Hz), 7.98 (s, 1H); 13C NMR (100 MHz, 49:1 DMSO-d6–D2O): d
28.6, 29.5, 29.9, 30, 30.2, 30.6, 39, 5, 39.7, 39.9, 40.2, 40.3, 40.6,
40.8, 50.4, 61.2, 62.4, 63, 63.2, 63.8, 64, 65.5, 69.6, 69.8, 71.4,
72.3, 72.5, 73.4, 75.8, 82.3, 101.7, 104.2, 124.7, 145.6, 172.1,
mixture was stirred under these conditions for 6 h until all starting
materials were consumed. The mixture was then neutralized with
Et3N, and filtered, and the filtrate was concentrated to dryness. The
residue was purified by silica gel column chromatography (2:1
EtOAc–petroleum ether) to give 10 (186 mg, 70%) as an amorphous
solid: ½a 2D5
ꢁ
ꢀ 12 (c 1, CHCl3); 1H NMR (400 MHz, CDCl3): d 1.35–
1.39 (m, 4H), 1.57–1.61 (m, 4H), 1.86, 2.00, 2.01, 2.06, 2.12 (5s,
15H), 2.57 (dd, 1H, J 12.8, 4.9 Hz), 3.27–3.29 (m, 3H), 3.46–3.48
(m, 1H), 3.79 (s, 3H), 3.91 (dd, 1H, J 10.5, 2.3 Hz), 4.09–4.11 (m,
2H), 4.80 (dd, 1H, J 12.3, 2.4 Hz), 5.17–5.19 (m, 1H), 5.25–5.27
(m, 1H), 5.36–5.38 (m, 1H), 5.41 (br d, 1H, J 10.0); 13C NMR
(100 MHz, CDCl3): d 18.8, 18.9, 19.1, 21.1, 23.7, 24.4, 26.7, 27.3,
35.5, 47.5, 49.4, 50.7, 60.5, 61.9, 66.6, 66.9, 69.8, 70.2, 74.8, 75.1,
75.4, 96.5, 165.6, 166.6, 168.2, 168.6, 168.8, 169.1. Anal. Calcd for
C26H40N4O13: C, 50.64; H, 6.54. Found: C, 50.51; H, 6.59. MALDI-
173.6; IR (KBr):
c = 3352, 2927, 2855, 1717, 1626, 1437, 1377,
1072, 1035 cmꢀ1. Anal. Calcd for C74H130N8O30S2: C, 53.03; H,
7.82. Found: C, 52.84; H, 7.87. MALDI-TOFMS: calcd for
C74H130N8O30S2: 1674.83 [M]; found: 1675.98 [M+H]+, 837.92
[(M+H)/2]+.
1.9. Synthesis of GNP (2)
TOFMS: calcd for C26H40N4O13
:
616.26 [M]+; found: 639.37
[M+Na]+.
To a solution of disulfide 1 (30 mg, 0.018 mmol) in Milli-Q H2O
(4 mL) was added HAuCl4ꢃ4H2O (22.11 mg). The solution was stir-
red at rt for 10 min, kept at 0 °C for 15 min, then NaBH4 (3.585 mg,
0.0087 mmol, in 0.5 mL H2O) was added in small portions under
vigorous stirring conditions. The reaction mixture turned immedi-
ately to deep brown. The mixture was kept under these conditions
for another 15 min, then warmed up to rt and stirred for further
3 h. At the end of this time, the solvent was removed by centrifu-
gation, and the black residue was redissolved in H2O (12 mL) and
purified by centrifugal filtering (40 min, 14,000 rpm). The process
was repeated three times. Finally, the H2O phase was lyophilized
to afford the gold glyconanoparticles 2 (10 mg) as a dark brown
powder. Average diameter and number of gold atoms: 3.4 nm,
976. 1H NMR (400 MHz, D2O): d 1.12–1.80 (m, 26H), 1.95–1.97
(m, 2H), 2.08–2.11 (m, 3H), 2.42 (dd, 1H, J 4.6, 1.8 Hz), 2.59 (dd,
1H, J 1.8, 2.1 Hz), 2.94 (t, 2H, J 8.3 Hz), 3.51 (br d, 1H, J 9.0 Hz),
3.59–3.96 (m, 12H), 4.16–4.19 (m, 2H), 4.48–4.50 (m, 1H), 8.10
1.7. 11-Thioacetylundecyl 3-O-[(methyl 5-acetamido-4,7,8,9-tet-
ra-O-acetyl-3,5-dideoxy-2-O- -glycero- -galacto-2-nonulopyr-
a-D
D
anosylhexanyl)triazol-1-methyl]-2,4,6-tri-O-benzoyl-b-D-galacto-
pyranoside (11)
To a suspension of 10 (266 mg, 0.43 mmol) and 8 (272 mg
0.4313 mmol) in 1:1 H2O–THF (40 mL) were added sodium ascor-
bate (34.18 mg, 0.17 mmol) and CuSO4ꢃ5H2O (21.4 mg,
0.086 mmol) under vigorous stirring. The mixture was stirred in
a dark room at 50–60 °C until complete consumption of the reac-
tants was indicated by TLC analysis. The solvent was evaporated,
and the residue was diluted with EtOAc, and washed with H2O
and brine. The aq layer was extracted with EtOAc, and the com-
bined organic layers were dried over Na2SO4 and concentrated.
Further purification was carried out by silica gel column chroma-
tography (3:1 EtOAc–petroleum ether) to give 11 (545 mg, 92%)
(s, 1H); IR (KBr):
c = 3395, 2928, 2855, 1711, 1635, 1415, 1118,
as a white amorphous solid: ½a D25
ꢁ
+ 70 (c 0.6, CHCl3); 1H NMR
1082, 1044. Found analytical data for 2: C, 23.70; H, 3.36.