3
3
1H, J ) 9.0 Hz), 5.56 (s, 1H), 5.19 (d, 1H, J ) 7.8 Hz), 5.17
(dd, 1H, 3J ) 4.8, 13.8 Hz), 5.12 (d, 1H, 3J ) 12 Hz), 5.02 (d, 1H,
by silica gel column chromatography (hexanes/EtOAc, 1:1f1:3)
to afford the pentasaccharide 16 as a white solid. A mixture of
16 (100 mg, 0.052 mmol), a 1 M solution of PMe3 in THF
(0.360 mL, 7 equiv), and 0.1 M NaOH (0.5 mL) in THF was stirred
at 60 °C overnight. The mixture was then concentrated and the
resulting residue was dissolved in DCM and extracted twice with
H2O. The organic layer was dried over Na2SO4 and concentrated
to dryness. The crude product was purified by silica gel column
chromatography (DCM f DCM/MeOH 8:1). The desired product
bearing a terminal free amine was obtained as an off-white solid.
Finally a mixture of this product (80 mg, 0.042 mmol) and Pd-
(OH)2 (80 mg) in DCM/MeOH/H2O/AcOH (1 mL:1 mL:2 mL:2
mL) was stirred at room temperature under atmospheric pressure
H2 for 24 h. The mixture was filtered through Celite, concentrated,
and extracted with DCM (3 times) and EtOAc (3 times). The water
layer was then lyophilized to afford a white solid, which was
purified by Sephadex G-10 size exclusion column. The pure LewisX
3J ) 8.4 Hz), 4.88 (m, 2H), 4.81 (t, 2H, J ) 10.2 Hz), 4.75 (d,
3
1H, 3J ) 10.8 Hz), 4.61 (d, 1H, 3J ) 4.8 Hz), 4.54-4.49 (m, 4H),
3
4.44-4.29 (m, 6H), 4.27 (d, 1H, J ) 11.4 Hz), 4.19-4.06 (m,
7H), 4.03-3.99 (m, 2H), 3.96 (s, 1H), 3.89 (dd, 1H, 3J ) 2.4, 10.2
3
Hz), 3.84-3.80 (m, 2H), 3.79 (s, 1H), 3.76 (d, 1H, J ) 4.8 Hz),
3.62 (d, 1H, 3J ) 10.2 Hz), 3.55 (dd, 1H, 3J ) 4.8, 10.2 Hz), 3.49-
3.43 (m, 2H), 3.41-3.37 (m, 5H), 3.32-3.29 (m, 4H), 3.28 (q,
3
3
1H, J ) 7.8, 9.0 Hz), 3.20 (d, 1H, J ) 10.8 Hz), 3.16 (s, 1H),
3
3
2.86 (d, 1H, J ) 8.4 Hz), 1.80-1.77 (m, 2H), 1.26 (d, 3H, J )
6.6 Hz); 13C NMR (150 MHz, CDCl3) δ 166.3, 164.9, 139.7, 139.7,
139.6, 139.2, 138.8, 138.6, 138.6, 138.5, 138.4, 138.2, 137.8, 130.1,
129.9, 129.5, 129.3, 128.9, 128.8, 128.7, 128.6, 128.5, 128.5, 128.4,
128.4, 128.3, 128.3, 128.3, 128.2, 128.1, 128.1, 128.1, 128.0, 127.9,
127.9, 127.9, 127.9, 127.8, 127.8, 127.7, 127.6, 127.4, 127.3, 127.2,
127.1, 127.0, 126.9, 126.4, 125.9, 103.6, 102.8 (1JC-H ) 163.4 Hz),
100.0 (1JC-H ) 161.3 Hz), 99.9 (1JC-H ) 158.2 Hz), 99.8 (1JC-H
) 164.6 Hz), 97.6 (1JC-H ) 174.1 Hz), 83.1, 82.2, 81.8, 79.2, 78.7,
77.5, 77.2, 77.0, 76.8, 76.2, 75.3, 75.2, 75.0, 74.9, 74.8, 74.1, 73.6,
73.5, 73.2, 73.0, 72.9, 71.6, 66.7, 66.6, 66.5, 48.5, 29.4, 16.5; HRMS
[M + Na]+ m/z calcd for C132H132N4NaO28 2244.8926, found
2244.8960.
pentasaccharide 1 was obtained in acetate form as a solid in 53%
1
yield over four steps. [R]25 -217 (c 0.5, H2O); H NMR (600
D
3
3
MHz, D2O) δ 4.94 (d, 1H, J ) 3.6 Hz), 4.52 (d, 1H, J ) 8.4
Hz), 4.33 (d, 1H, 3J ) 8.4 Hz), 4.28 (d, 1H, 3J ) 8.4 Hz), 4.25 (d,
3
3
1H, J ) 8.4 Hz), 3.97 (d, 1H, J ) 2.4 Hz), 3.80-3.75 (m, 4H),
3
3.73-3.69 (m, 4H), 3.63-3.37 (m, 20H), 3.31 (t, 1H, J ) 7.2
3
3-Aminopropyl â-D-galactopyranosyl-(1f4)-[(R-L-fucopyra-
nosyl)-(1f3)]-(2-N-acetamido-2-deoxy-â-D-glucopyranosyl)-(1f3)-
(â-D-galactopyranosyl)-(1f4)-â-D-glucopyranoside (1): The fully
protected pentasaccharide 11 (200 mg, 0.09 mmol) was mixed with
ethylenediamine (0.5 mL) in n-butanol (5 mL). The reaction was
stirred at 130 °C for 20 h. The mixture was then concentrated and
the residue was dissolved in DCM and extracted with a saturated
solution of NH4Cl. The organic layer was dried over Na2SO4 and
concentrated to dryness. The crude residue was purified by silica
gel column chromatography. The desired product was obtained in
its pure form as an off-white solid. The newly formed compound
was then dissolved in MeOH (5 mL) along with triethylamine (0.1
mL) and acetic anhydride (0.1 mL, 15 equiv). The reaction mixture
was stirred at room temperature for 4 h. It was then concentrated
and the residue was dissolved in DCM and extracted with a
saturated solution of NH4Cl. The organic layer was dried over Na2-
SO4 and concentrated to dryness. The crude residue was purified
Hz), 3.16-3.13 (m, 2H), 2.97 (t, 2H, J ) 7.2 Hz), 1.83 (s, 3H),
0.99 (d, 3H, J ) 6.0 Hz); 13C NMR (150 MHz, D2O) δ 181.7,
3
174.8, 103.0, 102.7, 102.2, 101.9, 98.7, 82.2, 78.4, 75.2, 75.1, 75.0,
74.9, 74.4, 73.1, 72.8, 72.6, 72.0, 71.1, 70.0, 69.3, 68.5, 68.4, 68.0,
67.8, 66.8, 61.6, 61.1, 60.1, 59.7, 56.1, 37.7, 26.8, 23.4, 22.4, 15.4;
HRMS [M + Na]+ m/z calcd for C35H62N2NaO25 933.3539, found
933.3531.
Acknowledgment. We are grateful for financial supports
from the University of Toledo, the National Institutes of Health
(R01-GM-72667), and the Pardee foundation.
Supporting Information Available: Experimental procedures
and selected 1H, 13C, and 2D NMR spectra. This material is
JO701694K
J. Org. Chem, Vol. 72, No. 23, 2007 8961