S. K. Madhusudan, A. K. Misra / Carbohydrate Research 340 (2005) 497–502
501
7.34 (m, 5H, aromatic); 13C NMR: d 21.0 (2C), 21.1
(3C), 26.6, 27.2, 54.3, 67.5, 67.9, 68.1, 68.7, 73.0, 73.5,
80.9, 82.1 (2C), 82.9, 102.4, 105.7, 112.3, 127.9–137.9
(aromatic), 169.8, 170.1, 170.2, 170.5, 170.6; [a]D À42
(c 1.2, CHCl3); ESI-MS: 682 (M, calcd); 700.4
(M+NH4+, found). Anal. Calcd for C32H42O16: C,
56.30; H, 6.20. Found: C, 56.19; H, 6.35.
1.27 (m, 10H, octyl), 1.57 (m, 2H, octyl), 2.09, 2.10
(2s, 9H, 3COCH3), 3.36–3.50 (m, 1H), 3.63–3.77 (m,
1H), 4.21–4.26 (m, 2H), 4.38–4.47 (m, 2H), 4.96–5.02
(m, 2H), 5.07 (br s, 1H); 13C NMR: d 14.3, 20.8 (2C),
21.0, 22.9, 26.3, 29.5 (2C), 29.7, 32.1, 63.7, 67.9, 77.6,
80.5, 81.7, 105.9, 169.9, 170.4, 170.8; [a]D +16.3 (c 1.5,
CHCl3); m/z: 389 [M+1]. Anal. Calcd for C19H32O8
(388): C, 58.75; H, 8.30. Found: C, 58.62; H, 8.46.
1.8. 3-O-Benzyl-1,2-O-isopropylidene-5,6-O-(2,3,4,5-
tetra-O-acetyl-D-arabinosylidene)-a-D-glucofuranose (2g)
1.12. Methyl 2,3,5,6-tetra-O-acetyl-b-D-glucofuranoside
(3d)
IR (neat): 3023, 2986, 2935, 1745, 1455, 1374, 1218,
1
1163, 1076, 1046, 760 cmÀ1; H NMR (CDCl3): d 1.30,
IR (neat): 3021, 2939, 2842, 1758, 1439, 1374, 1225,
1
1.47 (2s, 6H, CH(CH3)2), 1.99–2.11 (4s, 12H, 4COCH3),
3.99 (m, 1H), 4.10 (m, 3H), 4.22 (m, 1H), 4.30 (m, 1H),
4.52 (m, 1H), 4.63 (m, 2H), 4.98 (d, J = 3.6 Hz, 1H), 5.10
(m, 3H), 5.51 (dd, J = 7.6, 2.6 Hz, 1H), 5.88 (t,
J = 7.6 Hz each, 1H), 7.32–7.36 (m, 5H, aromatic); 13C
NMR: d 21.0 (4C), 26.6, 27.2, 62.1, 67.9, 68.6, 68.9,
70.1, 72.8, 73.4, 80.9, 82.1, 83.1, 102.0, 105.7, 112.3,
127.9–138.0 (aromatic), 169.8, 170.1, 170.2, 170.9; [a]D
À25 (c 1.3, CHCl3); ESI-MS: 610 (M, calcd); 628.3
(M+NH4+, found). Anal. Calcd for C29H38O14: C,
57.04; H, 6.27. Found: C, 56.90; H, 6.45.
1110, 1053, 930, 759 cmÀ1; H NMR (CDCl3): d 2.00,
2.06, 2.08, 2.11 (4s, 12H, 4COCH3), 3.41 (s, 3H,
OCH3), 4.12–4.21 (dd, J = 12.2, 4.8 Hz, 1H), 4.46–4.53
(dd, J = 9.3, 5.1 Hz, 1H), 4.60–4.67 (dd, J = 12.3,
2.3 Hz, 1H), 4.89 (br s, 1H), 4.99 (br s, 1H), 5.23–5.31
(m, 1H), 5.34 (d, J = 5.1 Hz, 1H); 13C NMR: d 21.0
(2C), 21.1 (2C), 56.2, 63.6, 69.2, 73.8, 78.6, 80.7, 107.9,
169.6, 169.9 (2C), 170.9; [a]D À32 (c 1.1, CHCl3); m/z:
363 [M+1]. Anal. Calcd for C15H22O10 (362): C, 49.72;
H, 6.12. Found: C, 49.83; H, 6.25.
1.13. Ethyl 2,3,5,6-tetra-O-acetyl-b-D-glucofuranoside
(3e)
1.9. Methyl 2,3,5-tri-O-acetyl-a-D-arabinofuranoside (3a)
IR (neat): 3023, 2941, 1748, 1441, 1372, 1222, 1110,
1
IR (neat): 3030, 2933, 2847, 1760, 1441, 1370, 1229,
1
1051, 954, 756 cmÀ1; H NMR (CDCl3): d 2.10, 2.12
1105, 1055, 930, 760 cmÀ1; H NMR (CDCl3): d 1.22–
(2s, 9H, 3COCH3), 3.40 (s, 3H, OCH3), 4.13–4.24 (m,
2H, H-5a,b), 4.39–4.49 (m, 1H, H-4), 4.93 (br s, 1H, H-
1), 4.98–5.02 (dd, J = 6.0, 1.4 Hz, 1H, H-3), 5.07 (d,
J = 1.4 Hz, 1H, H-2); 13C NMR (CDCl3): d 21.0 (3C),
55.3, 63.6, 76.8, 80.6, 81.6, 107.1, 169.9, 170.5, 170.9;
[a]D +48 (c 1.6, CHCl3); m/z: 291 [M+1]. Anal. Calcd
for C12H18O8 (290): C, 49.65; H, 6.25. Found: C,
49.57; H, 6.32.
1.33 (t, J = 7.2 Hz, 3H), 2.00, 2.06, 2.07, 2.10 (4s, 12H,
4COCH3), 2.64–2.68 (q, 2H), 4.10–4.19 (dd, J = 12.2,
5.2 Hz, 1H), 4.43–4.59 (m, 2H), 5.19–5.37 (m, 2H),
5.40–5.53 (m, 1H), 5.63 (d, J = 5.2 Hz, 1H); 13C NMR:
d 15.4, 20.8 (2C), 21.0 (2C), 25.8, 64.4, 69.2, 73.9, 78.3,
80.8, 106.5, 169.6, 170.1, 170.9; [a]D À23.8 (c 1.1,
CHCl3); m/z: 377 [M+1]. Anal. Calcd for C16H24O10
(376): C, 51.06; H, 6.43. Found: C, 50.88; H, 6.60.
1.10. Isopropyl 2,3,5-tri-O-acetyl-a-D-arabinofuranoside
(3b)
1.14. Methyl 2,3,5,6-tetra-O-acetyl-b-D-galactofurano-
side (3f)
IR (neat): 2976, 2936, 1744, 1438, 1372, 1231, 1039, 979,
900 cmÀ1; 1H NMR (CDCl3): d 1.15, 1.18, 1.20, 1.25 (4s,
6H, CH(CH3)2), 2.08, 2.10, 2.11 (3s, 9H, 3COCH3),
3.80–4.05 (m, 1H, CH(CH3)2), 4.20–4.28 (m, 2H, H-
IR (neat): 3021, 2941, 2840, 2370, 1757, 1439, 1373,
1216, 1108, 1054, 925, 758, 605 cmÀ1
;
1H NMR
(CDCl3): d 2.06, 2.09, 2.11, 2.14 (4s, 12H, 4COCH3),
3.38 (s, 3H, OCH3), 4.11–4.40 (m, 3H), 4.92 (br s,
1H), 5.02 (d, J = 5.8 Hz, 2H), 5,35–5.42 (m, 1H); 13C
NMR: d 19.9 (2C), 20.0 (2C), 54.3, 62.2, 69.1, 79.6,
80.8, 106.1, 169.7, 170.0, 170.2, 170.6; [a]D À43 (c 1.1,
CHCl3); m/z: 363 [M+1]. Anal. Calcd for C15H22O10
(362): C, 49.72; H, 6.12. Found: C, 49.85; H, 6.23.
5
a,b), 4.36–4.48 (m, 1H, H-4), 4.94–4.98 (m, 1H, H-3),
5.03 (d, J = 1.5 Hz, 1H, H-2), 5.12 (br s, 1H, H-1); 13C
NMR: d 20.8, 21.1, 21.7, 23.6 (2C), 63.7, 69.7, 77.4,
80.2, 82.2, 104.2; [a]D +26.9 (c 1.3, CHCl3); m/z: 319
[M+1]. Anal. Calcd for C14H22O8 (318): C, 52.82; H,
6.97. Found: C, 52.74; H, 7.12.
1.15. Ethyl 2,3,5,6-tetra-O-acetyl-b-D-galactofuranoside
(3g)
1.11. Octyl 2,3,5-tri-O-acetyl-a-D-arabinofuranoside (3c)
IR (neat): 2930, 2861, 2374, 1748, 1372, 1230,
1049 cmÀ1
IR (neat): 3020, 2946, 2835, 2367, 1760, 1441, 1375,
1219, 1108, 1050, 930, 758, 605 cmÀ1 1H NMR
;
;
1H NMR (CDCl3): d 0.88 (t, 3H, octyl),