Acetal-Linked Disaccharides and Trisaccharides
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909, 854, 762, 700, 667, 604 cm–1. ESI-MS: m/z = 764.5 [M +
NH4]+. C37H46O16 (746): calcd. C 59.51, H 6.21; found C 59.35, H
6.40.
1050, 758, 713 cm–1. ESI-MS: m/z = 792.3 [M + NH4]+. C37H42O18
(774): calcd. C 57.36, H 5.46; found C 57.15, H 5.59.
Methyl 2,3-Di-O-benzoyl-4,6-O-[(1R)-2,3,4,5-tetra-O-acetyl-
D-arab-
Methyl
2,3-Di-O-benzyl-4,6-O-[(1R)-2,3,4,5,6-penta-O-acetyl-
D-
inosylidene]-α- -glucopyranoside (18): Yellowish oil (414.0 mg;
D
70%). [α]2D5 = +62.5 (c = 0.1, CHCl3). 1H NMR (200 MHz,
CDCl3): δ = 1.64, 1.97, 2.02, 2.08 (4s, 12 H, 4 COCH3), 3.40 (s, 3
H, OCH3), 3.53–3.58 (m, 2 H), 4.01–4.05 (m, 1 H), 4.12–4.16 (m,
2 H), 4.19 (m, 1 H), 4.28–4.32 (m, 1 H), 4.53 (d, J = 6.4 Hz, 1 H),
5.10–5.12 (m, 2 H), 5.23–5.29 (m, 1 H), 5.51–5.54 (dd, J = 7.6,
2.0 Hz, 1 H), 5.95 (t, 1 H), 7.33–7.98 (m, 10 H, aromatic H) ppm.
13C NMR (75 MHz, CDCl3): δ = 20.3 (2 C), 21.1 (2 C), 55.9, 62.2,
62.5, 68.5 (2 C), 68.9, 69.6 (2 C), 72.4, 79.7, 98.3, 99.4, 128.7–133.8
(aromatic C), 165.5, 166.4, 169.6 (2 C), 170.3, 171.1 ppm. IR (neat):
glucosylidene]-α-
D-glucopyranoside (14): Yellowish oil (465.0 mg;
74%). [α]2D5 = +29.1 (c = 0.1, CHCl3). 1H NMR (200 MHz,
CDCl3): δ = 1.89, 1.96, 1.99, 2.01, 2.02 (5s, 15 H, 5 COCH3), 3.27–
3.34 (m, 1 H), 3.38 (s, 3 H, OCH3), 3.41–3.51 (m, 2 H), 3.64–3.71
(m, 1 H), 3.89–3.99 (t, J = 9.4 Hz each, 1 H), 4.03–4.12 (m, 2 H),
4.18–4.26 (dd, J = 14.0, 4.0 Hz, 1 H), 4.56 (d, J = 3.6 Hz, 1 H),
4.68–4.69 (dd, J = 10.0 Hz, 2 H), 4.79 (m, 1 H), 4.75–4.92 (dd, J
= 11.6, 12.0 Hz, 2 H), 5.05–5.16 (m, 2 H), 5.47–5.51 (dd, J = 7.6,
3.2 Hz, 1 H), 5.62–5.67 (dd, J = 6.8, 2.0 Hz, 1 H), 7.19–7.38 (m,
10 H, aromatic H) ppm. 13C NMR (75 MHz, CDCl3): δ = 20.9 (3
C), 21.1 (2 C), 55.9, 62.1, 62.3, 68.3, 68.9, 69.1, 69.6, 71.2, 74.1,
75.8, 78.9, 79.3, 82.1, 99.3, 99.6, 128.0–138.9 (aromatic C), 169.9
ν = 3020, 2927, 2856, 1733, 1454, 1372, 1275, 1219, 1103, 1052,
˜
759, 713, 668 cm–1. ESI-MS: m/z = 720.3 [M + NH4]+. C34H38O16
(702): calcd. C 58.12, H 5.45; found C 57.90, H 5.70.
(2 C), 170.9 (3C) ppm. IR (neat): ν = 2926, 1750, 1449, 1371, 1219,
˜
1052, 754, 700, 605 cm–1. ESI-MS: m/z = 764.4 [M + NH4]+.
Methyl 2,3-Di-O-benzyl-4,6-O-[(1S)-2,3,4,5,6-penta-O-acetyl-
D-gal-
actosylidene]-α- -galactopyranoside (19): Yellowish oil (458.0 mg;
D
C37H46O16 (746): calcd. C 59.51, H 6.21; found C 59.36, H 6.40.
73%). [α]2D5 = +40.1 (c = 0.1, CHCl3). 1H NMR (200 MHz,
CDCl3): δ = 2.01, 2.03, 2.05, 2.07, 2.10 (5s, 15 H, 5 COCH3), 3.33
(s, 3 H, OCH3), 3.62 (br.s, 1 H), 3.62–3.68 (dd, J = 12.0, 3.0 Hz, 1
H), 3.83–3.90 (m, 3 H), 4.00–4.08 (m, 2 H), 4.23–4.31 (dd, J = 11.6,
4.5 Hz, 1 H), 4.56 (d, J = 5.6 Hz, 1 H), 4.62 (m, 1 H), 4.68–4.86
(2dd, 4 H, 2PhCH2), 5.18–5.21 (m, 2 H), 5.26–5.32 (dd, J = 10.0,
4.0 Hz, 1 H), 5.64–5.70 (dd, J = 9.8, 1.2 Hz, 1 H), 7.26–7.40 (m,
10 H, aromatic H) ppm. 13C NMR (75 MHz, CDCl3): δ = 21.0 (2
C), 21.2 (3 C), 55.9, 62.7, 62.9, 66.9, 67.9, 68.0, 69.4, 69.5, 72.5,
74.3, 74.8, 75.8, 76.1, 98.3, 99.9, 127.7–139.1 (aromatic C), 169.7,
Methyl 2,3-Di-O-benzyl-4,6-O-[(1R)-2,3,4,5-tetra-O-acetyl-
D-arabi-
nosylidene]-α- -glucopyranoside (15): Yellowish oil (391.0 mg;
D
69%). [α]2D5 = +3.3 (c = 0.1, CHCl3). 1H NMR (200 MHz, CDCl3):
δ = 1.96, 2.03, 2.04, 2.10 (4s, 12 H, 4 COCH3), 3.32–3.34 (m, 1 H),
3.36 (s, 3 H, OCH3), 3.42–3.46 (m, 1 H), 3.47–3.49 (dd, J = 10.0,
2.0 Hz, 1 H), 3.68–3.70 (m, 1 H), 3.95 (t, J = 8.2 Hz each, 1 H),
4.10–4.21 (m, 3 H), 4.52–4.54 (m, 2 H), 4.61 (d, J = 12 Hz, 1 H),
4.75 (s, 2 H, PhCH2), 4.82 (d, J = 11.8 Hz, 1 H), 5.20 (m, 1 H),
5.26–5.28 (m, 1 H), 5.51–5.54 (dd, J = 7.6, 3.0 Hz, 1 H), 7.30–7.39
(m, 10 H, aromatic H) ppm. 13C NMR (75 MHz, CDCl3): δ = 21.0
(4 C), 55.8, 63.2 (2 C), 68.2 (2 C), 68.6, 69.5, 73.0, 74.8, 78.2, 79.0,
80.5, 99.7, 99.9, 127.9–138.2 (aromatic C), 170.1, 170.5, 171.2,
170.3, 170.7 (2 C), 170.8 ppm. IR (neat): ν = 3298, 3026, 2926,
˜
2859, 1730, 1451, 1373, 1223, 1050, 756, 701, 601 cm–1. ESI-MS:
m/z = 764.4 [M + NH4]+. C37H46O16 (746): calcd. C 59.51, H 6.21;
found C 59.35, H 6.42.
171.6 ppm. IR (neat): ν = 2926, 2857, 1750, 1457, 1374, 1220, 1162,
˜
1076, 858, 756, 701, 666, 606 cm–1. ESI-MS: m/z = 692.4 [M +
NH4]+. C34H42O14 (674): calcd. C 60.53, H 6.27; found C 60.35, H
6.50.
Methyl 2,3-Di-O-benzyl-4,6-O-[(1S)-2,3,4,5,6-penta-O-acetyl-
D-glu-
cosylidene]-β- -galactopyranoside (20): Yellowish oil (452.0 mg;
D
72%). [α]2D5 = +19.5 (c = 0.1, CHCl3). 1H NMR (200 MHz,
CDCl3): δ = 1.98, 2.01, 2.04, 2.05, 2.08 (5s, 15 H, 5 COCH3), 3.54
(s, 3 H, OCH3), 3.80–3.84 (dd, J = 10.0, 9.6 Hz, 1 H), 3.90–3.94
(m, 2 H), 4.16–4.20 (m, 4 H), 4.26–4.28 (d, J = 7.6 Hz, 1 H), 4.66
(br.s, 2 H, PhCH2), 4.70 (d, J = 2.0 Hz, 1 H), 4.82–4.89 (dd, J =
11.6, 12.0 Hz, 2 H, PhCH2), 5.20–5.29 (m, 3 H), 5.40–5.46 (m, 1
Methyl 2,3-Di-O-benzoyl-4,6-O-[(1R)-2,3,4,5,6-penta-O-acetyl-
D-
galactosylidene]-α- -glucopyranoside (16): Yellowish oil (488.0 mg;
D
75%). [α]2D5 = +76.6 (c = 0.01, CHCl3). 1H NMR (200 MHz,
CDCl3): δ = 1.57, 1.96, 2.03, 2.09, 2.17 (5s, 15 H, 5 COCH3), 3.38
(s, 3 H, OCH3), 3.50–3.63 (m, 2 H), 3.70–3.79 (dd, J = 8.0, 3.6 Hz,
1 H), 3.87–4.00 (m, 1 H), 4.19–4.29 (m, 2 H), 4.54 (d, J = 6.4 Hz,
1 H), 5.06–5.17 (m, 4 H), 5.21–5.23 (dd, J = 10.0, 2.0 Hz, 1 H),
5.40–5.46 (dd, J = 10.0, 1.2 Hz, 1 H), 5.87–5.96 (t, 1 H), 7.31–8.04
(m, 10 H, aromatic H) ppm. 13C NMR (75 MHz, CDCl3): δ = 20.5
(2 C), 20.9 (3 C), 55.8, 62.5 (2 C), 66.6, 67.8 (2 C), 68.9, 69.2,
69.4, 72.9, 79.4, 98.1, 99.2, 126.9–133.7 (aromatic C), 166.1, 166.3,
H), 5.70–5.73 (m, 1 H), 7.28–7.39 (m, 10 H, aromatic H) ppm. 13
C
NMR (75 MHz, CDCl3): δ = 18.0 (5 C), 57.1, 60.7, 62.3, 66.6, 68.1,
69.4, 70.5, 71.2, 72.1, 74.2, 75.5, 78.1, 79.5, 98.9, 105.1, 127.84–
139.5 (aromatic C), 170.0, 170.3 (2 C), 171.0, 171.6 ppm. IR (neat):
ν = 3466, 2927, 1748, 1373, 1222, 1054, 758, 700 cm–1. ESI-MS:
˜
m/z = 764.4 [M + NH4]+. C37H46O16 (746): calcd. C 59.51, H 6.21;
168.9–170.7 (5C) ppm. IR (neat): ν = 3022, 2979, 2933, 1754, 1753,
˜
1451, 1372, 1277, 1213, 1105, 1048, 764, 713, 668, 599 cm–1. ESI-
MS: m/z = 792.4 [M + NH4]+. C37H42O18 (774): calcd. C 57.36, H
5.46; found C 57.55, H 6.70.
found C 59.33, H 6.45.
Methyl 2,3-Di-O-benzyl-4,6-O-[(1S)-2,3,4,5-tetra-O-acetyl-
D-arabi-
nosylidene]-β-
D
-galactopyranoside (21): Yellowish oil (380.0 mg;
Methyl 2,3-Di-O-benzoyl-4,6-O-[(1R)-2,3,4,5,6-penta-O-acetyl-
D
-
67%). [α]2D5 = +2.7 (c = 0.1, CHCl3). 1H NMR (200 MHz, CDCl3):
δ = 1.97, 2.02, 2.06, 2.09 (4s, 12 H, 4 COCH3), 3.24 (br.s, 1 H),
3.43–3.45 (m, 1 H), 3.48–3.50 (dd, J = 9.6, 3.6 Hz, 1 H), 3.54 (s, 3
H, OCH3), 3.74 (d, J = 7.6 Hz, 1 H), 3.78–3.80 (dd, J = 6.9, 1.2 Hz,
glucosylidene]-α-D-glucopyranoside (17): Yellowish oil (507.0 mg;
78%). [α]2D5 = +98.3 (c = 0.1, CHCl3). 1H NMR (200 MHz,
CDCl3): δ = 1.78, 1.91, 1.95, 1.98, 2.01 (5s, 15 H, 5 COCH3), 3.33
(s, 3 H, OCH3), 3.52–3.57 (m, 2 H), 3.85–3.87 (m, 1 H), 4.01–4.03 1 H), 3.96 (d, J = 3.6 Hz, 1 H), 4.21–4.33 (m, 3 H), 4.56–4.62 (d,
(m, 1 H), 4.10–4.16 (m, 2 H), 4.63 (d, J = 4.2 Hz, 1 H), 4.99–5.02 J = 12.0 Hz, 1 H), 4.63 (d, J = 4.0 Hz, 1 H), 4.79–4.92 (3d, J =
(m, 1 H), 5.12–5.16 (m, 2 H), 5.20 (d, J = 3.7 Hz, 1 H), 5.39–5.48 12.0 Hz, 3 H, PhCH2), 5.18–5.21 (m, 1 H), 5.27–5.31 (dd, J = 5.4,
(m, 2 H), 5.87–5.96 (t, 1 H), 7.27–7.91 (m, 10 H, aromatic H) ppm. 2.8 Hz, 1 H), 5.56–5.62 (dd, J = 8.0, 2.2 Hz, 1 H), 7.31–7.40 (m,
13C NMR (75 MHz, CDCl3): δ = 20.8 (2 C), 21.0 (3 C), 55.9, 62.1, 10 H, aromatic H) ppm. 13C NMR (75 MHz, CDCl3): δ = 21.0 (5
62.4, 67.8, 68.8 (2 C), 69.6, 69.8, 70.7, 72.6, 79.4, 98.2, 99.6, 125.7–
133.8 (aromatic C), 165.8, 166.3, 169.7, 170.1, 170.2, 170.3,
C), 57.3, 62.4, 66.7, 68.7, 68.9, 69.3, 70.2, 71.6, 73.7, 75.4, 78.4,
79.3, 99.2, 104.9, 127.8–139.3 (aromatic C), 169.8, 170.0, 170.3,
170.9 ppm. IR (neat): ν = 2927, 2856, 1753, 1451, 1372, 1220, 1105,
171.0 ppm. IR (neat): ν = 3466, 3020, 2928, 2867, 1745, 1452, 1373,
˜
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Eur. J. Org. Chem. 2005, 3196–3205
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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