680
T. Nakae et al. / Bioorg. Med. Chem. 16 (2008) 675–682
raphy (EtOAc/MeOH or CH2Cl2/MeOH as the eluent)
to give the product and/or 8.
2.13H), 2.01 (s, 0.87H), 1.96 (s, 0.87H), 1.90 (s,
2.13H); FAB-HRMS (m/z): [M+H]+ calcd for
C22H32N5O12, 558.2048; found, 558.2075.
4.2.2.1. [2-(2-Nitro-1H-imidazol-1-yl)-N-methyl-acet-
amido]ethyl 2,3,4,6-tetra-O-acetyl-b-D-glucopyranoside
(5, TX-2244). Light yellow solid (8%); mp 67–69 ꢁC H
4.2.3. General procedure for deprotection. The mixture of
peracetylated glycoside and a small amount of sodium
methoxide in MeOH was stirred at room temperature.
After consumption of starting material, Dowex resin
(50W · 4, H+ form) was added and the precipitate was
filtered. The filtrate was evaporated under reduced pres-
sure. The residue was purified by silica gel column chro-
matography (CH2Cl2/MeOH, 4:1) to give the product.
1
NMR (CDCl3, 400 MHz): d 7.44 (d, J = 0.98 Hz,
0.67H), 7.19 (d, J = 0.98 Hz, 0.33H), 7.18 (d,
J = 0.98 Hz, 0.67H), 7.13 (d, J = 0.98 Hz, 0.33H),
5.40–4.98 (m, 5H), 4.52 (d, J = 8.1 Hz, 0.67H), 4.50 (d,
J = 7.8 Hz, 0.33H), 4.27 (dd, J = 4.4, 12.4 Hz, 1H),
4.19 (dd, J = 2.4, 4.4 Hz, 0.67H), 4.16 (dd, J = 2.4,
4.4 Hz, 0.33H), 4.11–4.07 (m, 0.67H), 3.98–3.93 (m,
0.33H), 3.76–3.62 (m, 3H), 3.56–3.50 (m, 1H), 3.16 (s,
2H), 2.96 (s, 1H), 2.09 (s, 2H), 2.08 (s, 1H), 2.06 (s,
1H), 2.04 (2s, 3H), 2.03 (s, 2H), 2.01 (s, 3H); FAB-
HRMS (m/z): [M+H]+ calcd for C22H31N4O13,
559.1888; found, 559.1909.
4.2.3.1. [2-(2-Nitro-1H-imidazol-1-yl)-N-methyl-acet-
amido]ethyl b-D-glucopyranoside (11, TX-2141). White
solid (64%); mp 89–91 ꢁC; 1H NMR (CD3CN, 400
MHz):
d
7.25(d, J = 1.2 Hz, 0.33H), 7.21 (d,
J = 1.2 Hz, 0.67H), 7.11 (d, J = 1.2 Hz, 0.33H), 7.10
(d, J = 0.98 Hz, 0.67H), 5.46 (d, J = 16.6 Hz, 0.67H),
5.40 (d, J = 16.6 Hz, 0.67H), 5.26 (s, 0.66H), 4.30 (d,
J = 7.6 Hz, 0.67H), 4.24 (d, J = 7.8 Hz, 0.33H), 3.95–
3.86 (m, 2H), 3.71–3.64 (m, 2H), 3.52–3.43 (m, 4.33H),
3.31–3.18 (m, 5.34H), 3.12 (s, 1H), 3.07–2.97 (m,
0.33H), 2.92 (s, 2H); FAB-HRMS: m/z [M + H]+ calcd
for C14H23N4O9, 391.1465; found, 391.1473; FT-IR
(KBr): 3384, 2892, 1654, 1543, 1493, 1416, 1369, 1299,
4.2.2.2. [2-(2-Nitro-1H-imidazol-1-yl)-N-methyl-acet-
amido]ethyl 2,3,4,6-tetra-O-acetyl-b-D-galactopyranoside
1
(6, TX-2245). Light yellow solid (7%); mp 74-76 ꢁC; H
NMR (CDCl3, 400 MHz): d 7.48 (d, J = 0.98 Hz,
0.67H), 7.19 (d, J = 1.2 Hz, 0.33H), 7.17 (d, J = 1.2
Hz, 0.67H), 7.12 (d, J = 0.98 Hz, 0.33H), 5.44–5.40 (m,
2H), 5.30–5.18 (m, 1H), 5.13 (d, J = 10.0 Hz, 0.67H),
5.09 (d, J = 10.0 Hz, 0.33H), 5.06–5.01 (m, 1H), 4.49
(d, J = 7.8 Hz, 0.67H), 4.48 (d, J = 7.8 Hz, 0.33H),
4.22 (dd, J = 6.6, 8.5 Hz, 0.67H), 4.19 (dd, J = 6.6,
8.5 Hz, 0.33H), 4.15–4.10 (m, 2H), 4.00–3.90 (m, 1H),
3.78–3.63 (m, 2H), 3.56–3.47 (m, 1H), 3.17 (s, 1H),
2.97 (s, 2H), 2.19 (s, 2H), 2.17 (s, 1H), 2.07 (s, 1H),
2.06 (s, 2H), 2.05 (s, 1H), 2.02 (s, 2H), 2.01 (s, 2H),
1.99 (s, 1H); FAB-HRMS (m/z): [M+H]+ calcd for
C22H31N4O13, 559.1888; found, 559.1907.
1162, 1078, 1034 cmꢀ1
.
4.2.3.2. [2-(2-Nitro-1H-imidazol-1-yl)-N-methyl-acet-
amido]ethyl b-D-galactopyranoside (12, TX-2218). White
solid (45%); mp 91–94 ꢁC; 1H MNR (CD3OD,
400 MHz): d 7.52 (d, J = 0.98 Hz, 0.67H), 7.42 (d,
J = 0.98 Hz, 0.33H), 7.16 (d, J = 0.98 Hz, 0.33H), 7.13
(d, J = 0.98 Hz, 0.67H), 5.68 (d, J = 16.6 Hz, 0.67H),
5.58 (d, J = 16.6 Hz, 0.67H), 5.46 (d, J = 16.6 Hz,
0.33H), 5.42 (d, J = 16.6 Hz, 0.33H), 4.31 (d,
J = 7.8 Hz, 0.67H), 4.22 (d, J = 7.1 Hz, 0.33H), 4.06–
3.93 (m, 1.67H), 3.82 (d, J = 2.2 Hz, 1H), 3.79–3.63
(m, 4H), 3.59–3.44 (m, 3.33H), 3.23 (s, 0.99H), 2.98 (s,
2.01H); FAB-HRMS: m/z [M+H]+ calcd for
C14H23N4O9, 391.1465; found, 391.1492; FT-IR (KBr):
3400, 2935, 1651, 1548, 1494, 1370, 1299, 1161,
4.2.2.3. [2-(2-Nitro-1H-imidazol-1-yl)-N-methyl-acet-
amido]ethyl 2,3,4,6-tetra-O-acetyl-a-D-mannopyranoside
(7, TX-2246). Light yellow solid (15%); mp 60-62 ꢁC; 1H
NMR (CDCl3, 400 MHz): d 7.46 (d, J = 0.98 Hz,
0.43H), 7.19 (2d, J = 1.2 Hz, 1H), 7.17 (d, J = 0.98 Hz,
0.57H), 5.36–5.28 (m, 3H), 5.26–5.18 (m, 2H), 4.89 (d,
J = 1.7 Hz, 0.43H), 4.82 (d, J = 1.7 Hz, 0.57H), 4.30
(dd, J = 5.4, 12.4 Hz, 0.43H), 4.25 (dd, J = 5.7,
12.3 Hz, 0.57H), 4.16–4.10 (m, 1H), 4.02–3.97 (m, 1H),
3.93–3.86 (m, 1H), 3.74–3.68 (m, 1H), 3.67–3.44 (m,
2H), 3.27 (s, 1.71H), 3.04 (s, 1.29H), 2.18 (s, 1.29H),
2.17 (s, 1.71H), 2.07 (s, 3H), 2.06 (s, 1.71H), 2.05 (s,
1.29H), 2.01 (s, 3H); FAB-HRMS (m/z): [M+H]+ calcd
for C22H31N4O13, 559.1888; found, 559.1901.
1075 cmꢀ1
.
4.2.3.3. [2-(2-Nitro-1H-imidazol-1-yl)-N-methyl-acet-
amido]ethyl a-D-mannopyranoside (13, TX-2217). White
solid (99%); mp 187–189 ꢁC; 1H NMR (CD3OD,
400 MHz): d 7.44 (d, J = 1.2 Hz, 0.5H), 7.40 (d,
J = 1.2 Hz, 0.5H), 7.17 (d, J = 1.2 Hz, 1H), 5.56–5.45
(m, 2H), 4.83 (d, J = 1.7 Hz, 0.5H), 4.76 (d,
J = 1.7 Hz, 0.5H), 4.02–3.98 (m, 0.5H), 3.93–3.86 (m.
2.5H), 3.85–3.47 (m, 7H), 3.23 (s, 1.5H), 3.00 (s,
1.5H); FAB-HRMS: m/z [M+H]+ calcd for
C14H23N4O9, 391.1465; found, 391.1444; FT-IR (KBr):
3383, 2938, 1649, 1544, 1495, 1414, 1371, 1299, 1226,
4.2.2.4. [2-(2-Nitro-1H-imidazol-1-yl)-N-methyl-acet-
amido]ethyl 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-b-D-
galactopyranoside (10, TX-2243). Light yellow solid
1
(37%); mp 90-92 ꢁC; H NMR (CDCl3, 400 MHz): d
7.56 (d, J = 0.98 Hz, 0.71H), 7.20 (d, J = 0.98 Hz,
0.29H), 7.17 (d, J = 0.98 Hz, 0.71H), 7.15 (d,
J = 0.98 Hz, 0.29H), 5.84 (d, J = 9.0 Hz, 1H), 5.40–
5.04 (m, 4H), 4.62 (d, J = 8.3 Hz, 0.71H), 4.49 (d,
J = 8.5 Hz, 0.29H), 4.27–4.10 (m, 4H), 4.02–3.83 (m,
1.71H), 3.77–3.64 (m, 1.71H), 3.52–3.47 (m, 0.29H),
3.39–3.32 (m, 0.29H), 3.17 (s, 0.87H), 2.95 (s, 2.13H),
2.17 (2s, 3H), 2.06 (s, 2.13H), 2.04 (s, 0.87H), 2.02 (s,
1137, 1063, 975, 845, 809, 682, 656, 637, 609 cmꢀ1
.
4.2.3.4. [2-(2-Nitro-1H-imidazol-1-yl)-N-methyl-acet-
amido]ethyl 2-acetamido-2-deoxy-b-D-galactopyranoside
1
(14, TX-2068). White solid (79%); mp 121–123 ꢁC; H
NMR (CD3OD, 400 MHz): d 7.72 (d, J = 1.2 Hz,
0.78H), 7.43 (d, J = 1.2 Hz, 0.22H), 7.17 (d,
J = 1.2 Hz, 0.22H), 7.15 (d, J = 1.2 Hz, 0.78H), 5.57