Molecules 2010, 15
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vacuo. The residue was purified with flash column chromatography (Isolera, SNAP KP-SIL, 5–95%
EtOAc in n-heptane, 22 min) to give 10 (0.528 g) in 82% yield.1H-NMR (CDCl3) δ 7.38–7.27 (m, 5H,
ArH), 5.08 (s, 2H, -COOCH2C-), 4.87 (s, 1H, -NH-), 3.60 (t, 2H, J = 6.5 Hz, -CH2OH), 3.23–3.09 (m,
2H, -CH2NH-), 1.59–1.45 (m, 4H, -CH2CH2OH, -CH2CH2NH-), 1.42–1.23 (m, 4H, 2 × -CH2CH2CH2-); 13C-
NMR (CDCl3) δ 156.6, 136.7, 128.6, 128.2, 66.7, 62.2, 41.0, 32.6, 30.0, 26.4, 25.4; MS(ES+)
calculated for C14H22NO (M+H) 252.16, found 252.42.
6-(Benzyloxycarbonylamino)-hexyl
6-O-benzyl-2,3-di-O-(4-fluorobenzoyl)-4-O-[2-(4-fluorophenyl-
sulfonyl)ethoxycarbonyl]-β-D-galactopyranoside (11). Compound 10 (0.118 g, 0.470 mmol), 8
(0.100 g, 0.118 mmol), and NIS (0.106g, 0.471 mmol) were dried under vacuum and in the absence of
light for 2 h. Distilled CH2Cl2 (5 mL) and TfOH (0.1 M in CH2Cl2, 0.001 mmol) were added and the
solution was stirred in room temperature in the absence of light for 2 h. The reaction mixture was
concentrated and the residue was purified with flash column chromatography (Isolera, SNAP KP-SIL,
5–95% EtOAc in n-heptane, 22 min) giving 11 (0.064 g) in 83% yield.1H-NMR (CDCl3) δ 8.02–7.86
(m, 6H, ArH), 7.39–7.24 (m, 12H, ArH), 7.11–6.99 (m, 4H, ArH), 5.56 (dd, 1H, J = 8.0 and 10.3 Hz,
H-2), 5.44 (d, 1H, J = 3.3 Hz, H-4), 5.37 (dd, 1H, J = 3.3 and 10.3 Hz, H-3), 5.09 (s, 2H,
-COOCH2Ph), 4.65 (d, 1H, J = 8.0 Hz, H-1), 4.51 (q, 2H, J = 11.9 and 26.7 Hz, -OCH2Ph), 4.29 (t, 2H,
J = 5.7 Hz, -COOCH2CH2-), 3.96 (t, 1H, J = 6.5 Hz, H-5), 3.92–3.85 (m, 1H, -OCHHCH2CH2-),
3.67–3.62 (m, 1H, H-6), 3.60–3.53 (m, 1H, H-6), 3.52–3.44 (m, 1H, -OCHHCH2CH2-), 3.39–3.30 (m,
2H, -COOCH2CH2-), 3.10–3.01 (m, 2H, -NHCH2-), 1.58–1.44 (m, 2H, -OCH2CH2CH2-), 1.35–1.13
(m, 6H, -CH2CH2CH2NH-); 13C-NMR (CDCl3) δ 167.4 (J = 8.6 Hz), 167.2, 164.9 (J = 6.5 Hz), 164.7,
164.4, 164.3, 156.4, 154.0, 137.6, 136.7, 135.3 (J = 5.3 Hz), 132.3 (J = 4.2 and 9.2 Hz), 131.2
(J = 9.8 Hz), 128.5 (J = 7.2 Hz), 128.2, 127.9, 127.8, 125.6 (J = 4.7 Hz), 125.1 (J = 4.3 Hz), 117.0,
116.8, 115.7 (J = 15.9 and 22.1 Hz), 101.2 (C-1), 77.2, 73.6, 72.3, 71.9, 71.8, 69.9, 69.7, 67.4, 66.7,
61.3, 54.9, 40.9, 29.7, 29.3, 26.8, 25.5; 19F-NMR (CDCl3) δ -103.0, -104.6, -105.2; MS(ES+)
calculated for C50H51F3NO14S (M+H) 978.30, found 978.46.
6-(Benzyloxycarbonylamino)hexyl 6-O-benzyl-2,3-di-O-(4-fluorobenzoyl)-β-D-galactopyranoside (12).
Compound 11 (0.013 g, 0.013 mmol) was dissolved in THF (13 mL) and TBAF in THF
(0.015 mL, 0.015 mmol) was added. The solution was stirred at room temperature for 11 min and
purification by preparative HPLC (30–100% CH3CN in H2O, 50 min) afforded 12 (7.2 mg) in 72%
yield.1H-NMR (CDCl3) δ 8.07–7.96 (m, 4H, ArH), 7.38–7.28 (m, 10H, ArH), 7.08–6.99 (m, 4H, ArH),
5.72 (dd, 1H, J = 8.0 and 10.3 Hz, H-2), 5.25 (dd, 1H, J = 3.1 and 10.3 Hz, H-3), 5.09 (s, 2H,
-COOCH2), 4.72 (t, 1H, J = 5.8 Hz), 4.63 (d, 1H, J = 8.0 Hz, H-1), 4.61 (d, 2H, J = 3.1 Hz, -OCH2Ph),
4.38 (d, 1H, J = 2.9 Hz, H-4), 3.96–3.87 (m, 1H, -OCHHCH2-), 3.86–3.78 (m, 3H), 3.54–3.46 (m, 1H,
-OCHHCH2-), 3.05 (s, 2H, -CH2CH2NH-), 1.60–1.41 (m, 2H, -OCH2CH2CH2-), 1.36–1.10 (m, 6H,
-OCH2CH2CH2CH2CH2CH2NH-); 13C-NMR (CDCl3) δ 167.4 (J = 16.5 Hz), 164.8 (J = 16.4 Hz),
164.8 (J = 53.8 Hz), 137.5, 132.6 (J = 9.5 Hz), 132.4 (J = 9.4 Hz), 128.7, 128.3, 128.1, 125.9 (J = 2.8
Hz), 125.5 (J = 2.8 Hz), 115.8 (J = 22.1 Hz), 115.7 (J = 22.1 Hz), 101.6, 74.5, 74.0, 73.3, 70.1, 70.0,
69.4, 68.4, 66.9, 41.0, 29.7, 29.3, 26.3, 25.6; 19F-NMR (CDCl3) δ -105.1, -105.5; MS(ES+) calculated
for C41H44F2NO10 (M+H) 748.29, found 748.40.