MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
´
DAHMEN, MAGNUSSON, AND HANSEN
196
filtered through celite. Pyridine (0.5 mL) was added, and the mixture was concen-
trated with toluene. The residue was O-acetylated in acetic anhydride/pyridine (1:1, 60
mL). After 19 h the mixture was concentrated and co-evaporated with toluene.
Crystallization from methanol gave 10 (968 mg, 84%), mp 156–159°C; [a]D20 +65°
(c 1.0, CHCl3); 1H NMR (CDCl3): d 8.07–8.13 (2 H, Ar), 7.68–7.88 (4 H, Ar),
7.43–7.63 (3 H, Ar), 5.73 (dd, 1 H, J 8.7, 10.6 Hz, H-3), 5.44 (dd, 1 H, J 8.0, 10.2
Hz, H-20), 5.36 (d, 1 H, J 2.8 Hz, H-40), 5.31, (d, 1 H, J 8.5 Hz, H-1), 5.15–5.23 (m,
2 H, H-100, H-200), 4.95 (dd, 1 H, J 3.4 Hz, 10.6 Hz, H-300), 4.81 (dd, 1 H, J 1.4 Hz,
3.2 Hz, H-400), 4.65 (d, 1 H, J 7.7 Hz, H-10), 4.31 (dd, 1 H, J 2.0 Hz, 11.6 Hz, H-6),
4.03–4.25 (m, 4 H, incl. H-2, H-6), 4.01 (dd, 1 H, J 3.2 Hz, 10.2 Hz, H-30), 3.96 (bt,
1 H, J 6.9 Hz, H-500), 3.73–3.90 (m, 5 H, H-4, H-50, H-600, –OCH2aCH2TMS), 3.65–
3.73 (m, 1 H, H-5), 3.45 (dt, 1 H, J 6.7 Hz, ).8 Hz, –OCH2bCH2TMS), 2.17, 2.06,
2.05, 2.02, 1.99, 1.92, 1.87 (7 Â s, 24 H, 8Â Ac), 0.64–0.83 (m, 2 H, –CH2TMS),
À 0.18 (s, 9 H, –SiMe3); 13C NMR (CDCl3): d 170.8, 170.64, 170.57, 170.4, 170.3,
170.2, 169.7, 164.8, 134.2, 130.4, 129.2, 129.0, 123.9, 101.3, 97.7, 93.9, 76.9, 73.8, 72.8,
71.6, 71.1, 70.8, 68.0, 67.7, 67.2, 67.0, 66.9, 64.9, 62.6, 61.7, 61.4, 55.4, 21.22, 21.2, 21.1,
21.08, 21.0, 20.9, 18.1, À 1.2; HRMS calcd for C54H67O26NSi (M + Na): 1196.3618,
found 1196.3624.
1,3,6-Tri-O-acetyl-2-deoxy-2-phthalimido-4-O-(4,6-di-O-acetyl-2-O-benzoyl-3-O-
(2,3,4,6-tetra-O-acetyl-a-D-galactopyranosyl)-b-D-galactopyranosyl]-b-D-glucopyra-
nose (11). To a solution of 10 (100.5 mg, 0.086 mmol) in dry toluene (1 mL) and
acetic anhydride (0.125 mL) was added boron trifluoride etherate (0.016 mL, 0.127
mmol) and the mixture was stirred under argon. After 3 h a saturated aqueous sol-
ution of NaHCO3 (10 mL) was added, and the mixture was extracted with ethyl
acetate, dried and concentrated. The residue crystallized when standing. Recrystalliza-
tion from ethanol gave 11 (87.2 mg, 92%), mp 189–193°C; [a]D21 +87° (c 1.0,
1
CDCl3); H NMR (CDCl3): d 8.07–8.12 (2 H, Ar), 7.70–7.88 (4 H, Ar), 7.43–7.63
(3 H, Ar), 6.43 (d, 1 H, J 8.9 Hz, H-1), 5.83 (dd, 1 H, J 8.4 Hz, 10.5 Hz, H-3), 5.44
(dd, 1 H, J 7.8 Hz, 10.1 Hz, H-20), 5.36 (d, 1 H, J 2.6 Hz, H-40), 5.15–5.23 (m, 2 H,
H-100, H-200), 4.95 (dd, 1 H, J 3.4 Hz, 10.5 Hz, H-300), 4.82 (dd, 1 H, J 1.3 Hz, 3.3
Hz, H-400), 4.65 (d, 1 H, J 7.8 Hz, H-10), 4.33 (dd, 1 H, J 9.0 Hz, 10.5 Hz, H-2),
4.24–4.29 (m, 2 H), 3.72–4.16 (m, 9 H, incl. H-30, H-500, H-4), 2.17, 2.07, 2.04, 2.02,
1.98, 1.96, 1.94, 1.86, 1.84 (9 Â s, 27 H, 9 Â Ac); 13C NMR (CDCl3): d 170.9, 170.8,
170.7, 170.6, 170.3, 170.2, 170.1, 169.7, 168.9, 167.9, 164.8, 134.9, 134.3, 130.4,
129.2, 128.9, 124.2, 101.0, 94.0, 89.9, 76.1, 73.8, 73.7, 71.2, 70.9, 70.7, 68.0, 67.2,
67.0, 66.9, 65.0, 62.2, 61.6, 61.5, 54.1, 21.22, 21.2, 21.18, 21.13, 21.1, 21.07, 21.0,
20.9, 20.86; HRMS calcd for C51H57O27NNa (M+ Na): 1138.3016, found 1138.3005.
2-(Methoxycarbonyl)ethyl 3,6-di-O-acetyl-2-deoxy-2-phthalimido-1-thio-4-O-(4,6-di-
O-acetyl-2-O-benzoyl-3-O-(2,3,4,6-tetra-O-acetyl-a-D-galactopyranosyl)-b-D-galacto-
pyranosyl]-b-D-glucopyranoside (12). Crude 11 (5.1 mg, 0.005 mmol) was co-
evaporated with dry toluene, dissolved in dry dichloromethane (0.5 mL) and methyl
3-mercaptopropionate (0.0015 mL, 0.014 mmol) was added. The reaction mixture was
cooled to 0°C under argon and boron trifluoride etherate (0.003 mL, 0.028 mmol) was
added. After 1 h at 0°C the mixture was stirred at ambient temperature. After 24 h
dichloromethane was added and the mixture was washed with a saturated aqueous
solution of NaHCO3 (10 mL), dried, and concentrated, followed by co-evaporation