Synthesis of Gold Glyconanoparticles
FULL PAPER
CH2), 5.06 (bt, 1 H, H4), 5.22 and 5.34 (2 m, each 1 H, CO-
ppm. High-resolution MS data of C39H44O17 (784.258): [M ϩ H]
3
OCH2CHϭCH2), 5.72 [d, J(H1,H2) ϭ 8.1 Hz, 1 H, H1], 5.89 (m, found 785.265, calculated 785.266.
1 H, COOCH2CHϭCH2) ppm. 13C NMR (75.4 MHz, CDCl3): δ ϭ
Allyl (2,4,6-Tri-O-acetyl-β-D-glucopyranosyl)-(1Ǟ3)-2,4-di-O-ben-
20.7 (COCH3), 61.5 (C6), 68.9 (COOCH2CHϭCH2), 67.7, 70.1,
72.7, and 76.8 (C2, C3, C4, and C5), 91.7 (C1), 118.9 (CO-
OCH2CHϭCH2), 133 (COOCH2CHϭCH2) ppm. High-resolution
MS data of C18H24O12 (432.127): [M ϩ NH4] found 450.162, calcu-
lated 450.161.
zoyl-α-
L
-fucopyranoside (37): To solution of 36 (0.25 g,
a
0.32 mmol) in THF (4 mL) and morpholine (0.16 mL) tetrakis(tri-
phenylphosphane)palladium (53 mg, 55 µmol) was added at 65 °C.
The mixture was stirred at 65 °C for 2 h, when TLC (CH2Cl2/ace-
tone, 9:1) showed the complete conversion of 36 into 37 (Rf ϭ
0.22). The mixture was diluted with CH2Cl2, washed with 10% aq.
NaCl, dried, filtered, and concentrated. Column chromatography
(CH2Cl2/acetone, 85:15) of the residue afforded 37, isolated as
yellow syrup (0.21 g, 93%). [α]2D0 ϭ Ϫ106 (c ϭ 0.5, CHCl3). 1H
2,4,6-Tri-O-acetyl-3-O-allyloxycarbonyl-α-
D-glucopyranosyl
Tri-
chloroacetimidate (35): To a solution of 34 (1.2 g, 2.67 mmol) in
dry DMF (4 mL) hydrazine acetate (0.38 g, 4.13 mmol) was added
and the mixture was stirred for 1 h, when TLC (CH2Cl2/acetone,
9:1) showed the disappearance of 34 and the formation of a new
spot (Rf ϭ 0.46). The solution was diluted with EtOAc, washed
with water and 10% aq. NaCl, dried, filtered, and concentrated. To
a solution of the residue in dry CH2Cl2 (6 mL) and trichloroaceto-
nitrile (2.8 mL, 26.7 mmol) 1,8-diazabicyclo[5.4.0]undec-7-ene (44
µL, 0.267 mmol) was added at 0 °C, and the mixture was stirred for
2 h, then concentrated. Column chromatography (CH2Cl2/acetone,
95:5) of the residue yielded 35, isolated as yellow syrup (0.88 g,
3
NMR (300 MHz, CDCl3): δ ϭ 1.21 [d, J(H5,H6) ϭ 6.5 Hz, 3 H,
CMe], 1.57, 2.01, and 2.06 (3 s, each 3 H, 3 Ac), 3.95 [dd,
3J(H5Ј,H6aЈ) ϭ 2.7, 3J(H6aЈ,H6bЈ) ϭ 12.3 Hz, 1 H, H6aЈ], 4.03
3
and 4.20 (2 m, each 1 H, OCH2CHϭCH2), 4.61 [d, J(H1Ј,H2Ј) ϭ
7.7 Hz, 1 H, H1Ј], 4.67 (bt, 1 H, H2Ј), 4.82 (bt, 1 H, H4Ј), 5.13
3
and 5.26 (2 m, each 1 H, OCH2CHϭCH2), 5.29 [bd, J(H3,H4) ϭ
3
3
3.7, J(H4,H5) Ͻ 1 Hz, 1 H, H4], 5.44 [dd, J(H2,H3) ϭ 10.4 Hz,
1 H, H3], 5.64 [d, 3J(H1,H2) ϭ 3.0 Hz, 1 H, H1], 5.81 (m, 1 H,
OCH2CHϭCH2), 7.45, 7.55, and 8.10 (3 m, 4 H, 4 H, and 2 H, 2
PhCO) ppm. 13C NMR (75.4 MHz, CDCl3): δ ϭ 16.2 (C6), 19.9,
20.6, and 20.7 (3 COCH3), 62.4 (C6Ј), 68.8 (OCH2CHϭCH2), 65.1,
69.4, 70.7, 71.1, 71.7, 72.3, and 74.1 (C2, C3, C4, C2Ј, C3Ј, C4Ј,
and C5Ј), 95.9 and 97.9 (C1 and C1Ј), 117.4 (OCH2CHϭCH2),
165.9 and 166.2 (2 PhCO), 170.3, 170.7, and 171.0 (3 COCH3)
ppm. High-resolution MS data of C35H40O15 (700.237): [M ϩ Na]
found 723.226, calculated 723.227.
60%). [α]2D0 ϭ ϩ85 (c ϭ 1, CHCl3). H NMR (300 MHz, CDCl3):
1
δ ϭ 2.02, 2.05, and 2.07 (3 s, each 3 H, 3 Ac), 4.13 [dd,
3
3J(H5,H6a) ϭ 1.7, J(H6a,H6b) ϭ 12.0 Hz, 1 H, H6a], 4.19 (m, 1
H, H5), 4.27 [dd, 3J(H5,H6b) ϭ 4.0 Hz, 1 H, H6b], 4.63 (m, 2
3
3
H, COOCH2CHϭCH2), 5.13 [dd, J(H1,H2) ϭ 3.6, J(H2,H3) ϭ
10.1 Hz, 1 H, H2], 5.23 (bt, 1 H, H4), 5.29 and 5.34 (2 m, each 1
H, COOCH2CHϭCH2), 5.39 (bt, 1 H, H3), 5.89 (m, 1 H, CO-
OCH2CHϭCH2), 6.58 (d, 1 H, H1), 8.69 [s, 1 H, C(NH)CCl3] ppm.
13C NMR (75.4 MHz, CDCl3): δ ϭ 28.9, 29.1, and 29.2 (3
COCH3), 63.7 (C6), 70.0 (COOCH2CHϭCH2), 69.0, 70.1, 71.1,
and 74.4 (C2, C3, C4, and C5), 90.5 (C1), 112.6 (COOCH2CHϭ
CH2), 123.0 (COOCH2CHϭCH2), 155.3, 155.6, and 156.3 (3
COCH3) ppm.
Allyl (Sodium 2,4,6-tri-O-acetyl-3-O-sulfonato-β-
D-glucopyranosyl)-
(1Ǟ3)-2,4-di-O-benzoyl-α- -fucopyranoside (38): To a solution of
L
37 (0.12 g, 0.17 mmol) in dry DMF (7 mL), sulfur trioxide trimeth-
ylamine complex (0.94 g, 6.8 mmol) was added at 50 °C. The mix-
ture was stirred at 50 °C for 48 h, when TLC (CH2Cl2/MeOH, 9:1)
showed the conversion of 37 into nonsodiated 38 (Rf ϭ 0.35). After
quenching of the reaction with MeOH (10 mL), the solution was
co-concentrated with toluene. A solution of the residue in CH2Cl2
(50 mL) was washed with saturated aq. NaHCO3, dried, filtered,
and concentrated. The residue dissolved in MeOH (10 mL), con-
taining Dowex 50 W ϫ 8 Naϩ resin, was stirred for 15 min, then
filtered and concentrated. Column chromatography (CH2Cl2/
MeOH, 85:15) of the residue gave 38, isolated as a yellow, amorph-
Allyl (2,4,6-Tri-O-acetyl-3-O-allyloxycarbonyl-β-D-glucopyranosyl)-
(1Ǟ3)-2,4-di-O-benzoyl-α-L-fucopyranoside (36): A solution of allyl
2,4-di-O-benzoyl-α--fucopyranoside[10] (0.24 g, 0.58 mmol) and 35
(0.48 g, 0.87 mmol) in dry CH2Cl2 (3 mL), containing activated
˚
molecular sieves (4 A, 0.4 g), was stirred at room temperature for
30 min. Then, TMSOTf (8.2 µL, 43.5 µmol) was added, and the
mixture was stirred for 20 min, when TLC (hexane/EtOAc, 2:1)
showed the formation of a new product (Rf ϭ 0.13). The mixture
was neutralized with triethylamine, filtered, and the solution was
washed with 10% aq. NaCl, dried, filtered, and concentrated. Col-
umn chromatography (hexane/EtOAc, 2:1) of the residue afforded
36, isolated as white foam (0.27 g, 60%). [α]2D0 ϭ Ϫ57 (c ϭ 1,
CHCl3). 1H NMR (500 MHz, CDCl3; 2D TOCSY): δ ϭ 1.21 [d,
3J(H5,H6) ϭ 6.4 Hz, 3 H, CMe], 1.52, 1.99, and 2.01 (3 s, each
3 H, 3 Ac), 3.71 (m, 1 H, H5Ј), 3.95 [dd, 3J(H5Ј,H6aЈ) ϭ 2.5,
3J(H6aЈ,H6bЈ) ϭ 12.2 Hz, 1 H, H6aЈ], 4.03 and 4.22 (2 m, each 1
1
ous powder (73 mg, 53%). [α]2D0 ϭ Ϫ96 (c ϭ 1, CHCl3). H NMR
(500 MHz, CDCl3; 2D TOCSY): δ ϭ 1.18 [d, 3J(H5,H6) ϭ 6.6 Hz,
3 H, CMe], 1.61, 1.88, and 1.89 (3 s, each 3 H, 3 Ac), 3.59 (m, 1
3
3
H, H5Ј), 3.72 [dd, J(H5Ј,H6aЈ) ϭ 1.4, J(H6aЈ,H6bЈ) ϭ 12.2 Hz,
1 H, H6aЈ], 4.02 and 4.19 (2 dd, each 1 H, OCH2CHϭCH2), 4.09
3
[dd, J(H5Ј,H6bЈ) ϭ 5.5 Hz, 1 H, H6bЈ], 4.26 (m, 1 H, H5), 4.37
(bt, 1 H, H3Ј), 4.53 [dd, 3J(H1,H2) ϭ 3.2, 3J(H2,H3) ϭ 10.4 Hz, 1
H, H2], 4.58 [d, 3J(H1Ј,H2Ј) ϭ 7.9 Hz, 1 H, H1Ј], 4.83 (bt, 1 H,
H4Ј), 5.12 and 5.28 (2 m, each 1 H, OCH2CHϭCH2), 5.29 [bd,
3J(H3,H4) ϭ 3.7, 3J(H4,H5) Ͻ 1 Hz, 1 H, H4], 5.40 (dd, 1 H, H3),
5.57 (d, 1 H, H1), 5.83 (m, 1 H, OCH2CHϭCH2), 7.41, 7.54, and
8.07 (3 m, 4 H, 4 H, and 2 H, PhCO) ppm. 13C NMR (75.4 MHz,
CDCl3): δ ϭ 16.6 (C6), 20.4, 21.0, and 21.1 (3 COCH3), 62.8 (C6Ј),
69.2 (OCH2CHϭCH2), 65.5, 69.8, 71.1, 71.5, 72.0, 72.7, and 74.6
(C2, C3, C4, C2Ј, C3Ј, C4Ј, and C5Ј), 96.3 and 98.2 (C1 and C1Ј),
117.8 (OCH2CHϭCH2), 134.1 (OCH2CHϭCH2) ppm. High-reso-
lution MS data of C35H39NaO18S (802.175): [M ϩ Na] found
825.162, calculated 825.165.
3
H, COOCH2CHϭCH2), 4.18 (m, 1 H, H5), 4.51 (d, J ϭ 5.5 Hz,
2 H, OCH2CHϭCH2), 4.61 [dd, 3J(H1,H2) ϭ 3.0, 3J(H2,H3) ϭ
3
10.7 Hz, 1 H, H2], 4.76 [d, J(H1Ј,H2Ј) ϭ 7.9 Hz, 1 H, H1Ј], 4.81
(bt, 1 H, H2Ј), 4.95 (bt, 1 H, H3Ј), 5.00 (bt, 1 H, H4Ј), 5.12, 5.18,
5.24, and 5.27 (4 m, each 1 H, COOCH2CHϭCH2 and OCH2CHϭ
CH2), 5.29 [bd, 3J(H3,H4) ϭ 3.7, 3J(H4,H5) Ͻ 1 Hz, 1 H, H4],
5.44 (dd, 1 H, H3), 5.61 (d, 1 H, H1), 5.81 (m, 2 H, COOCH2CHϭ
CH2 and OCH2CHϭCH2), 7.45, 7.57, and 8.09 (3 m, 4 H, 4 H,
and 2 H, 2 PhCO) ppm. 13C NMR (75.4 MHz, CDCl3): δ ϭ 16.3
(C6), 62.3 (C6Ј), 68.5 and 68.7 (COOCH2CHϭCH2 and
OCH2CHϭCH2), 65.2, 68.5, 69.5, 70.8, 71.1, 71.7, 72.7, and 77.1
(C2, C3, C4, C5, C2Ј, C3Ј, C4Ј, and C5Ј), 95.9 and 98.2 (C1 and
Allyl (Sodium 3-O-sulfonato-β-
D-glucopyranosyl)-(1Ǟ3)-α-L-fuco-
pyranoside (39): To a solution of 38 (70 mg, 87 µmol) in MeOH
C1Ј), 117.4 and 118.7 (COOCH2CHϭCH2 and OCH2CHϭCH2) (5 mL) and water (0.5 mL) sodium methoxide (pH 10) was added.
Eur. J. Org. Chem. 2004, 4323Ϫ4339
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim