54
J. Ohlsson, G. Magnusson / Carbohydrate Research 329 (2000) 49–55
gave an analytical sample; mp 163–164 °C (lit.
[26] 150–151 °C). H NMR (CDCl3): l 8.15–
56.0. HRMS calcd for C68H64NaO15 (M+
1
Na): 1143.4143, found: 1143.4159.
4-Methoxyphenyl
h - - galactopyranosyl) - (14) - 2,3,6 - tri - O-
benzoyl-i- -galactopyranoside (10).—Com-
(2,3,4,6-tetra-O-acetyl-
7.95 (m, 6 H, Ph), 7.65–7.35 (m, 9 H, Ph),
5.73 (dd, 1 H, J 7.7, 10.6 Hz, H-2), 5.50 (ABq,
2 H, J 9.2, 11.9 Hz, H-3%, 4%), 5.34 (dd, 1 H, J
3.0, 10.7 Hz, H-3), 5.24 (m, 2 H, H-1%, 2%), 4.84
(d, 1 H, J 3.9 Hz, H-1), 4.75 (dd, 1 H, J 7.2,
11.4 Hz, H-6), 4.60 (t, 1 H, J 7.2 Hz, H-5%),
4.54 (dd, 1 H, J 6.2, 11.5 Hz, H-6), 4.43 (d, 1
H, J 2.1 Hz, H-4), 4.20 (ddd, 1 H, J 5.1, 6.9,
4.4 Hz, OCH2CH2Br), 4.13 (m, 1 H, H-5),
3.90 (m, 2 H, H-6%, OCH2CH2Br), 3.65 (dd, 1
H, J 6.2, 11.0 Hz, H-6%), 3.50 (m, 2 H,
OCH2CH2Br), 2.09, 2.06, 2.01, 1.88 (4 s, 3 H
each, OAc).
D
D
pound 9 (174 mg, 0.155 mmol) was dissolved
in AcOH (4 mL) and hydrogenolyzed (H2,
10% Pd–C, 50 mg) for 24 h. The mixture was
filtered through Celite and concd. The residue
was dissolved in pyridine (2.0 mL), Ac2O (2.0
mL) was added, and the mixture was stirred
overnight, then concd and flash chro-
matographed (SiO2, 1:1, heptane–EtOAc) to
give 10 (130 mg, 90%). Recrystallization from
10:1 EtOAc–Et2O gave an analytical sample;
mp 205–207 °C; [h]2D3 +104° (c 1.0, CHCl3).
1H NMR (CDCl3): l 8.07–7.95 (m, 6 H, Ph),
7.65–7.36 (m, 9 H, Ph), 7.00 (d, 2 H, J 9.1 Hz,
Ph), 6.72 (d, 2 H, J 9.1 Hz, Ph), 5.96 (dd, 1 H,
J 7.7, 10.6 Hz, H-2), 5.50 (m, 2 H, H-3%, 4%),
4.39 (dd, 1 H, J 3.0, 10.6 Hz, H-3), 5.26 (m, 1
H, H-2%), 5.22 (d, 1 H, J 3.0 Hz, H-1%), 5.20 (d,
1 H, J 7.8 Hz, H-1), 4.79 (dd, 1 H, J 7.7, 11.4
Hz, H-6), 4.62 (m, 2 H, H-6, 5%), 4.48 (d, 1 H,
J 2.5 Hz, H-4), 4.37 (m, 1 H, H-5), 3.90 (dd,
1 H, J 7.7, 10.9 Hz, H-6%), 3.75 (s, 3 H, OMe),
3.72 (dd, 1 H, J 6.1, 11.0 Hz, H-6%), 2.17, 2.10,
2.01, 1.92 (4 s, 3 H each, OAc). 13C NMR
(CDCl3): l 171.0, 170.8, 170.6, 170.2, 166.6,
166.5, 165.6, 156.1, 151.5, 134.2, 133.9, 133.7,
130.4, 130.2, 130.1, 129.8, 129.7, 129.1, 129.0,
128.9, 119.3, 114.9, 101.4, 99.0, 76.2, 73.9,
73.3, 69.7, 68.8, 68.2, 67.9, 67.8, 63.2, 61.3,
56.0, 21.3, 21.10, 21.05, 21.0. HRMS calcd for
C48H48NaO19 (M+Na): 951.2687, found:
951.2669.
References
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Immunol., 155 (1995) 2427–2432.
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G. Noori, K. Pa˚lsson, Carbohydr. Res., 113 (1983) 219–
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Carlstro¨m, Carbohydr. Res., 127 (1984) 15–25.
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245–250.
2-Bromoethyl (2,3,4,6-tetra-O-acetyl-h-
galactopyranosyl)-(14)-2,3,6-tri-O-benzoyl-
i- -galactopyranoside (11).—To a soln of 1
D
-
D
(2.42 g, 2.65 mmol) and N-iodosuccinimide
(715 mg, 3.19 mmol) in CH2Cl2 (100 mL) at
0 °C was added 2-bromoethanol (0.38 mL,
5.30 mmol) and trimethylsilyl trifluoro-
methanesulfonate (0.052 mL, 0.27 mmol). The
mixture was stirred for 10 min at 0 °C, diluted
with CH2Cl2 (200 mL), washed with 10% aq
Na2S2O3 (50 mL) and satd aq NaHCO3 (2×
25 mL), dried (Na2SO4), and concd. The
residue was flash chromatographed (SiO2,
4:11:1 heptane–EtOAc gradient) to give 11
(2.31 g, 95%). Recrystallization from MeOH
[18] P.J. Garegg, H. Hultberg, C. Lindberg, Carbohydr. Res.,
83 (1980) 157–162.