G. Mugunthan et al. / Carbohydrate Research 346 (2011) 1760–1766
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3.5.3. (2S)-2,3-Dihydro-(20,30-O-isopropylidene-
erythrofuranosyl)-6-nitro-imidazo[2,1-b]thiazole (20)
Yield 25–30%; Pale yellow solid; mp 187–188 °C; [
a
-D
-
J = 6.8 Hz, J = 14.0 Hz, 1H, H-4), 3.92 (dd, J = 3.4 Hz, J = 8.7 Hz, 1H,
H-6a), 3.89 (dd, J = 3.4 Hz, J = 8.7 Hz, 1H, H-6b), 3.46 (s, 3H,
–OCH3), 3.35 (d, J = 5 Hz, 1H, –OH), 1.45, 1.33 (2 ꢂ s, 2 ꢂ 3H, –C–
(CH3)2); 13C NMR (100 MHz, CDCl3) d 147.65, 137.09, 120.53,
112.23, 105.25, 83.49, 81.24, 79.77, 67.59, 57.90, 51.93, 26.80,
26.27; IR (Neat) mmax 3340, 2985, 2937, 2833, 1547, 1494, 1377,
1337, 1290, 1217, 1077, 1020, 853, 824 cmꢁ1; MALDI-TOF MS:
a
]D ꢁ184.5 (c
1, CHCl3); 1H NMR (400 MHz, CDCl3) d 7.81 (s, 1H, Ar-H), 4.82 (dd,
J = 3.4 Hz, J = 6.1 Hz, 1H, H-30), 4.74 (dd, J = 3.8 Hz, J = 6.1 Hz, 1H, H-
20), 4.53–4.47 (m, 2H, H-5 and H-3a), 4.35–4.30 (m, 1H, H-3b), 4.07
(d, J = 10.8 Hz, 1H, H-40a), 3.65 (dd, J = 3.8 Hz, J = 9.5 Hz, 1H, H-10),
3.55 (dd, J = 3.5 Hz, J = 10.8 Hz, 1H, H-40b), 1.50, 1.34 (2 ꢂ s,
2 ꢂ 3H, –C(CH3)2); 13C NMR (100 MHz, CDCl3) d 147.76, 137.13,
120.72, 112.79, 81.46, 80.90, 80.59, 80.10, 72.78, 68.81, 51.41,
25.88, 24.46; IR (Neat) mmax 3089, 2981, 2919, 2849, 1514, 1454,
1381, 1340, 1298, 1205, 1165, 1107, 1060, 853 cmꢁ1; MALDI-TOF
MS: m/z calcd for C12H15N3O5S: 313.3. Found: 336.4 [M+Na]+,
m/z calcd for C13H19N3O7: 329.3. Found: 352.3 [M+Na]+ 368.3
,
[M+K]+
.
3.5.8. 3,6-Anhydro-1-deoxy-4,5-O-isopropylidene-1-[N-(4-
nitroimidazolo)]-
Yield 60%; Pale yellow solid; mp 144.5–145.5 °C; [
1, CHCl3); 1H NMR (400 MHz, CDCl3)
7.90, 7.50 (2 ꢂ d,
D-mannitol (24)
a
]
D
ꢁ50.2 (c
352.4 [M+K]+
d
.
J = 1.5 Hz, 2H, Ar-H), 4.82 (dd, J = 3.4 Hz, J = 6.1 Hz, 1H, H-5), 4.76
(dd, J = 4 Hz, J = 6.1 Hz, 1H, H-4), 4.32 (d, J = 12 Hz, 1H, H-1a),
4.20–4.11 (m, 2H, H-2 and H-1b), 4.08 (d, J = 10.8 Hz, 1H, H-6a),
3.55 (dd, J = 3.4 Hz, J = 10.8 Hz, 1H, H-6b), 3.23 (dd, J = 4 Hz,
J = 8.3 Hz, 1H, H-3), 3.17 (d, J = 2.7 Hz, 1H, –OH), 1.49, 1.34 (2 ꢂ s,
2 ꢂ 3H, –C(CH3)2); 13C NMR (100 MHz, CDCl3) d 147.76, 137.13,
120.72, 112.79, 81.46, 80.90, 80.59, 80.10, 72.78, 68.82, 51.41,
25.88, 24.46; IR (Neat) mmax 3392, 2985, 2938, 2862, 1542, 1519,
3.5.4. (2R)-2,3-Dihydro-(20,30-O-isopropylidene-
erythrofuranosyl)-6-nitro-imidazo[2,1-b]thiazole (21)
Yield 20–25%; Pale yellow solid; mp 191–192 °C; [
a-D-
a
]
D ꢁ1.3 (c 1,
CHCl3); 1H NMR (400 MHz, CDCl3) d 7.76 (s, 1H, Ar-H), 4.87 (dd,
J = 3.5 Hz, J = 6.1 Hz, 1H, H-30), 4.76–4.69 (m, 2H, H-20 and H-2),
4.47 (dd, J = 8.1 Hz, J = 11.5 Hz, 1H, H-3a), 4.16 (dd, J = 7.8 Hz,
J = 11.5 Hz, 1H, H-3b), 4.11 (d, J = 10.9 Hz, 1H, H-40a), 3.79 (dd,
J = 3.8 Hz, J = 8.2 Hz, 1H, H-10), 3.59 (dd, J = 3.6 Hz, J = 10.9 Hz, 1H,
H-40b), 1.50, 1.32 (2 ꢂ s, 2 ꢂ 3H, –C(CH3)2); 13C NMR (100 MHz,
CDCl3) d 150.84, 150.37, 117.19, 113.23, 83.03, 81.42, 79.86,
72.79, 51.05, 48.49, 25.79, 24.45; IR (Neat) mmax 3150, 2987,
2949, 2927, 1526, 1504, 1474, 1463, 1383, 1340, 1281, 1202,
1094, 1054, 1028, 981, 856 cmꢁ1; MALDI-TOF MS: m/z calcd for
1493, 1380, 1338, 1290, 1209, 1165, 1094, 989, 858, 824 cmꢁ1
;
MALDI-TOF MS: m/z calcd for C12H17N3O6: 299.2. Found: 322.5
[M+Na]+, 338.5 [M+K]+.
3.5.9. 3,6-Anhydro-1-deoxy-4,5-O-isopropylidene-1-[N-(4-
nitroimidazolo)]-D-glucitol (25)
C
12H15N3O5S: 313.3. Found: 336.4 [M+Na]+, 352.4 [M+K]+
Yield 78%; Pale yellow solid; mp 113–114 °C; [
a
]
ꢁ46.7 (c 1,
.
CHCl3); 1H NMR (400 MHz, CDCl3) d 7.90, 7.52 (2 ꢂDd, J = 1.4 Hz,
2H, Ar-H), 4.85 (dd, J = 3.6 Hz, J = 6.1 Hz, 1H, H-5), 4.75 (dd,
J = 3.8 Hz, J = 6.1 Hz, 1H, H-4), 4.31–4.26 (m, 1H, H-2), 4.23–4.18
(m, 2H, H-1a,b), 4.12 (d, J = 10.8 Hz, 1H, H-6a), 3.57 (br s, 1H,
–OH), 3.52 (dd, J = 3.6 Hz, J = 10.8 Hz, 1H, H-6b), 3.30 (pt,
J = 4.3 Hz, J = 4.5 Hz, 1H, H-3), 1.51, 1.34 (2 ꢂ s, 2 ꢂ 3H,
–C(CH3)2); 13C NMR (100 MHz, CDCl3) d 136.79, 120.32, 113.01,
81.33, 81.16, 80.74, 72.52, 69.84, 50.77, 25.79, 24.19; IR (Neat) mmax
3412, 3144, 2985, 2927, 2855, 1543, 1492, 1382, 1338, 1290, 1208,
1097, 858 cmꢁ1; MALDI-TOF MS: m/z calcd for C12H17N3O6: 299.2.
3.5.5. (2S)-2,3-Dihydro-[(40R)-10,20-O-isopropylidene-30-O-
methyl-b-L-threofuranos-40-yl]-6-nitro-imidazo[2,1-b]oxazole
(22)
Yield 53%; Pale yellow glassy solid; [
a
]
ꢁ64.2 (c 1, CHCl3); 1H
D
NMR (400 MHz, CDCl3) d 5.92 (d, J = 3.6 Hz, 1H, H-10), 5.53–5.48
(m, J = 8.6 Hz, 1H, H-2), 4.62 (d, J = 3.6 Hz, 1H, H-20), 4.59 (pt,
J = 3.7 Hz, 1H, H-40), 4.39 (dd, J = 6.5 Hz, J = 10.8 Hz, 1H, H-3a),
4.26 (dd, J = 8.6 Hz, J = 10.8 Hz, 1H, H-3b), 3.91 (d, J = 3.52 Hz, 1H,
H-30), 3.45 (s, 3H, –OCH3), 1.49, 1.33 (2 ꢂ s, 2 ꢂ 3H, –C(CH3)2);
13C NMR (100 MHz, CDCl3) d 156.00, 147.13, 112.72, 112.57,
105.50, 84.12, 83.79, 81.12, 79.52, 58.08, 45.42, 26.87, 26.21; IR
(Neat) mmax 3137, 2978, 2938, 2833, 1597, 1525, 1472, 1374,
1318, 1279, 1163, 1080, 1030, 977 cmꢁ1; MALDI-TOF MS: m/z
calcd for C13H17N3O7: 327.2. Found: 328.4 [M+H]+.
Found: 322.5 [M+Na]+, 338.567 [M+K]+
.
3.5.10. 3,6-Anhydro-1-deoxy-4,5-O-isopropylidene-1-[N-(2-
nitroimidazolo)]-D-glucitol (26)
Yield 72%; Pale yellow solid; mp 127 °C; [
a
]
ꢁ34.0 (c 0.5,
D
CHCl3); 1H NMR (400 MHz, CDCl3) d 7.25, 7.11 (2 ꢂ d, J = 1.0 Hz,
2H, Ar-H), 4.85–4.80 (m, 2H, H-5 and H-4), 4.75 (dd, J = 2.0 Hz,
J = 13.6 Hz, 1H, H-1a), 4.55 (dd, J = 8.4 Hz, J = 13.6 Hz, 1H, H-1b),
4.44–4.42 (m, 1H, H-2), 4.13 (d, J = 10.8 Hz, 1H, H-6a), 3.75 (br s,
1H, –OH), 3.53 (dd, J = 3.2 Hz, J = 10.8 Hz, 1H, H-6b), 3.44 (pt,
J = 3.1 Hz, 1H, H-3), 1.51, 1.33 (2 ꢂ s, 2 ꢂ 3H, –C(CH3)2); 13C NMR
(100 MHz, CDCl3) d 127.89, 127.78, 112.82, 81.55, 81.05, 80.74,
72.56, 68.89, 52.85, 25.67, 23.97; IR (Neat) mmax 3391, 2986,
2940, 2850, 1538, 1488, 1363, 1278, 1210, 1164, 1102, 1062,
988 cmꢁ1; MALDI-TOF MS: m/z calcd for C12H17N3O6: 299.2.
3.5.6. 3,6-Anhydro-1-deoxy-4,5-O-isopropylidene-1-[N-(2,4-
dinitroimidazolo)]-D-glucitol (17)
Yield 70%; colorless solid; mp 172.5–173.5 °C; [a]D +28.5 (c 0.5,
MeOH); 1H NMR (400 MHz, DMSO) d 8.70 (s, 1H, Ar-H), 5.52 (d,
J = 5.4 Hz, 1H, –OH), 4.82–4.78 (m, 2H, H-5 and H-1a), 4.68 (dd,
J = 3.64 Hz, J = 6.12 Hz, 1H, H-4), 4.46 (dd, J = 9 Hz, J = 13.5 Hz, 1H,
H-1b), 4.16–4.09 (m, 1H, H-2), 3.85 (d, J = 10.7 Hz, 1H, H-6a),
3.39–3.34 (m, 2H, H-6b and H-3), 1.38, 1.24 (2 ꢂ s, 2 ꢂ 3H,
–C(CH3)2); 13C NMR (100 MHz, DMSO) d 141.90, 141.80, 127.18,
111.03, 83.15, 80.81, 79.42, 71.50, 67.36, 52.41, 25.73, 24.38; IR
(KBr) mmax 3561, 3151, 2941, 2868, 1541, 1489, 1374, 1334, 1276,
1210, 1092, 1064, 1024, 988, 858, 820, 753 cmꢁ1; MALDI-TOF
MS: m/z calcd for C12H16N4O8: 344.2. Found: 367.4 [M+Na]+,
Found: 300.5 [M+H]+
.
3.5.11. 3,6-Anhydro-1-deoxy-4,5-O-isopropylidene-1-[N-(2-
nitroimidazolo)]-D-mannitol (27)
383.4 [M+K]+
Yield 80%; Pale yellow solid; mp 146 °C; [
a
]
D ꢁ49 (c 0.5, CHCl3);
.
1H NMR (400 MHz, CDCl3) d 7.21, 7.11 (2 ꢂ d, J = 1.5 Hz, 2H, Ar-H),
4.95 (dd, J = 2.7 Hz, J = 14 Hz, 1H, H-1a), 4.81 (dd, J = 3.4 Hz,
J = 6.1 Hz, 1H, H-5), 4.76 (dd, J = 3.9 Hz, J = 6.1 Hz, 1H, H-4), 4.46
(dd, J = 7.8 Hz, J = 14 Hz, 1H, H-1b), 4.26 (dt, J = 2.7 Hz, J = 8 Hz,
1H, H-2), 4.10 (d, J = 10.8 Hz, 1H, H-6a), 3.53 (dd, J = 3.5 Hz,
J = 10.8 Hz, 1H, H-6b), 3.31(dd, J = 3.9 Hz, J = 5.2 Hz, 1H, H-3), 2.80
(br s, 1H, –OH), 1.48, 1.33 (2 ꢂ s, 2 ꢂ 3H, –C(CH3)2); 13C NMR
3.5.7. 6-Deoxy-1,2-O-isopropylidene-3-O-methyl-6-[N-(4-
nitroimidazolo)]-a-D-glucofuranose (23)
Yield 54%; Pale yellow glassy solid; [
a
]
ꢁ40.3 (c 1, CHCl3); 1H
NMR (400 MHz, CDCl3) d 7.88, 7.48 (2 ꢂDd, J = 1.5 Hz, 2H, Ar-H),
5.91 (d, J = 3.7 Hz, 1H, H-1), 4.63 (d, J = 3.7 Hz, 1H, H-2), 4.32 (dd,
J = 2.2 Hz, J = 14.0 Hz, 1H, H-3), 4.21–4.19 (m, 1H, H-5), 4.11 (dd,