A. Steinmann, J. Thimm, J. Thiem
FULL PAPER
1 H, 4ЈЈ-H), 5.29 (d, 1 H, 1-H), 5.21 (d, 1 H, 1Ј-H), 5.10 (dd, 1 H,
104.10 (C-2Ј), 102.16 (C-1ЈЈ), 92.12 (C-1), 79.00 (C-5), 75.59 (C-2),
2ЈЈ-H), 5.04 (m, 1 H, 2-H), 5.01 (m, 1 H, 4-H), 4.99 (m, 1 H, 3ЈЈ- 75.16 (C-4Ј), 74.98 (C-3Ј), 71.93 (C-4ЈЈ), 71.48 (C-5ЈЈ), 71.02 (C-
H), 4.96, (m, 1 H, 2Ј-H), 4.93 (vt, 1 H, 4-H), 4.40 (d, 1 H, 1ЈЈ-H), 3ЈЈ), 68.98 (C-5), 68.76 (C-4), 68.14 (C-2ЈЈ), 67.16 (C-3), 65.48,
4.21 (m, 1 H, 5-H), 4.13 (vt, 1 H, 3Ј-H), 4.08 (m, 2 H, 6ЈЈ-Ha, 6ЈЈ- 63.04, 62.48, 61.63 (C-6, C-1Ј, C-6Ј, C-6ЈЈ), 21.20–20.73 (m, CH3)
Hb), 4.01 (m, 2 H, 6Ј-Ha, 6Ј-Hb), 4.00 (m, 2 H, 6-Ha, 6-Hb), 3.95
(vt, 1 H, 5Ј-H), 3.87 (vt, 1 H, 5ЈЈ-H), 1.98–2.11 (m, 3 H, CH3) ppm;
J1ЈЈ,2ЈЈ = 7.9, J2ЈЈ,3ЈЈ = 10.4, J3ЈЈ,4ЈЈ = 2.4, J4ЈЈ,5ЈЈ Ͻ 1, J5ЈЈ,6ЈЈa = 6.3,
J5ЈЈ,6ЈЈb = 6.6, J1Ј,2Ј = 4.1, J2Ј,3Ј = 9.5, J3Ј,4Ј = 9.4, J4Ј,5Ј = 10.1, J5Ј,6Јa
= 6.3, J5Ј,6Јb = 6.0, J6Јa,6Јb = 11.9, J1,2 = 3.8, J2,3 = 9.8, J3,4 = 9.8 Hz.
13C NMR (100 MHz, CDCl3): δ = 169.48–170.47 (m, C=O), 101.61
(C-1ЈЈ), 91.96 (C-1Ј), 91.81 (C-1), 75.92 (C-3Ј), 71.11 (C-5ЈЈ), 70.50
(C-3), 67.18 (C-4ЈЈ), 62.38 (C-6ЈЈ), 61.52 (C-6), 61.05 (C-6Ј), 21.16–
20.92 (m, CH3) ppm.
ppm.
2,3,4,6-Tetra-O-acetyl-β-
D
-galactopyranosyl-(1Ǟ3)-2,4,6-tri-O-ace-
-fructofuranoside
-galactopyranosyl-(1Ǟ3)-2,4,6-tri-
-glucopyranosyl 1,3,4,6-Tetra-O-acetyl-β- -fructofur-
anoside (15), and 2,3,4,6-Tetra-O-acetyl-β- -galactopyranosyl-
(1Ǟ6)-2,3,4-tri-O-acetyl-α- -glucopyranosyl 1,3,4,6-Tetra-O-ace-
tyl-β- -fructofuranoside (16): H NMR (400 MHz, CDCl3): δ =
tyl-α-
(14), 2,3,4,6-Tetra-O-acetyl-β-
O-acetyl-α-
D-glucopyranosyl 1,3,4,6-Tetra-O-acetyl-β-D
D
D
D
D
D
1
D
4.74 (d, 1 H, 1-H), 4.63 (d, 1 H, 1-H), 4.78 (d, 1 H, 1-H) ppm.
GC-MS fragmentation.
2,3,4,6-Tetra-O-acetyl-β-D-galactopyranosyl-(1Ǟ4)-2,3,6-tri-O-ace-
tyl-α- -glucopyranosyl 2,3,4,6-Tetra-O-acetyl-α-
D
D
-glucopyranoside
2,3,4,6-Tetra-O-acetyl-β-
D
-galactopyranosyl-(1Ǟ1Ј)-2,3,4,6-tetra-
-fructofurano-
(10): 1H NMR (400 MHz, CDCl3): δ = 5.50 (vt, 1 H, 3-H), 5.47
(vt, 1 H, 3Ј-H), 5.35 (d, 1 H, 4ЈЈ-H), 5.26 (d, 1 H, 1Ј-H), 5.22 (d, 1
H, 1-H), 5.12 (dd, 1 H, 2ЈЈ-H), 5.04 (m, 1 H, 2Ј-H), 5.03 (m, 1 H,
4Ј-H), 4.96 (dd, 1 H, 3ЈЈ-H), 4.95 (m, 1 H, 2-H), 4.50 (d, 1 H, 1ЈЈ-
H), 4.32 (d, 1 H, 6-Hb), 4.21 (m, 1 H, 6Ј-Hb), 4.15 (m, 1 H, 6-Ha),
4.13 (m, 1 H, 6ЈЈ-Ha), 4.10 (m, 1 H, 6ЈЈ-Hb), 4.03 (m, 1 H, 6Ј-Ha),
4.02 (m, 1 H, 5Ј-H), 3.94 (m, 1 H, 5-H), 3.90 (vt, 1 H, 5ЈЈ-H), 3.73
(vt, 1 H, 4-H), 2.16, 2.10, 2.08, 2.07, 2.06, 2.06, 2.05, 2.05, 2.02,
O-acetyl-α- -glucopyranosyl 3,4,6-Tri-O-acetyl-β-
D
D
side (17): 1H NMR (400 MHz, CDCl3): δ = 5.67 (d, 1 H, 1-H),
5.41–5.45 (m, 2 H, 3ЈЈ-H, 4ЈЈ-H), 5.35 (m, 1 H, 3-H), 5.26 (d, 1 H,
4Ј-H), 5.16 (dd, 1 H, 2-ЈH), 5.02 (m, 1 H, 3Ј-H), 5.01 (m, 1 H, 4-
H), 4.84 (dd, 1 H, 2-H), 4.53 (d, 1 H, 1Ј-H), 4.26–3.97 (m, 9 H, 5-
H, 5Ј-H, 5ЈЈ-H, 6-Ha, 6Ј-Ha, 6ЈЈ-Ha, 6-Hb, 6Ј-Hb, 6ЈЈ-Hb), 3.75
(d, 1 H, 1ЈЈ-Ha), 3.46 (d, 1 H, 1ЈЈ-Hb), 2.15, 2.14, 2.12, 2.11, 2.09,
2.06, 2.06 2.04, 2.04, 2.03, 2.01 (11 s, 11 ϫ 3 H, 11 CH3) ppm; J1,2
= 3.7, J2,3 = 10.4, J1Јa,1Јb = 10.7, J1ЈЈ,2ЈЈ = 7.5, J2ЈЈ,3ЈЈ = 8.2, J3ЈЈ,4ЈЈ
Ͻ 1, J4ЈЈ,5ЈЈ = 3.0 Hz. 13C NMR (100 MHz, CDCl3): δ = 101.21 (C-
2ЈЈ), 101.95 (C-1Ј), 90.01 (C-1), 82.32 (C-5ЈЈ), 75.24 (C-3ЈЈ), 73.57
(C-4ЈЈ), 71.27 (C-3Ј), 71.09 (C-2), 71.03 (C-3), 70.32 (C-1ЈЈ), 69.12
(C-2Ј), 68.63 (C-4), 68.86 (C-5), 68.78 (C-5Ј), 67.36 (C-4Ј), 63.32,
62.01, 61.59 (C-6, C-6Ј, C-6ЈЈ), 171.10, 170.91, 170.64, 170.63,
170.56, 170.52, 170.47, 170.26, 170.18, 170.04, 169.95 (11 C=O),
21.10–21.03 (m, CH3) ppm.
2.02, 1.96 (11 s, 11 ϫ 3 H, 11 CH3) ppm; J1ЈЈ,2ЈЈ = 7.9, J2ЈЈ,3ЈЈ
10.1, J3ЈЈ,4ЈЈ = 3.2, J4ЈЈ,5ЈЈ Ͻ 1, J5ЈЈ,6ЈЈa = 7.2, J5ЈЈ,6ЈЈb = 5.3, J1Ј,2Ј
3.8, J2Ј,3Ј = 10.1, J3Ј,4Ј = 10.1, J5Ј,6Јb = 5.5, J6Јa,6Јb = 11.7, J1,2
=
=
=
3.8, J2,3 = 9.1, J3,4 = 9.5, J4,5 = 9.8, J5,6a Ͻ 1, J6a,6b = 11.7 Hz. 13C
NMR (100 MHz, CDCl3): δ = 171.02, 170.81, 170.59, 170.51,
170.35, 170.20, 170.06, 169.70, 169.67, 169.30, 169.28 (11 ϫ C=O),
101.80 (C-1ЈЈ), 92.14 (2 C, C-1Ј, C-1), 77.28 (C-4), 71.47 (C-5ЈЈ),
71.11 (C-2), 70.66 (C-3ЈЈ), 70.40, 70.36 (C-3Ј, C-3), 70.24 (C-2Ј),
69.69 (C-2ЈЈ), 69.39 (C-4Ј), 68.95 (C-5), 68.49 (C-5Ј), 66.93 (C-4ЈЈ),
62.23 (C-6Ј), 62.18 (C-6), 61.14 (C-6ЈЈ), 21.11–20.94 (m, CH3) ppm.
2,3,4,6-Tetra-O-acetyl-β-
D
-galactopyranosyl-(1Ǟ3Ј)-2,3,4,6-tetra-
-fructofurano-
O-acetyl-α- -glucopyranosyl 1,4,6-Tri-O-acetyl-β-
D
D
side (18): 1H NMR (400 MHz, CDCl3): δ = 5.75 (d, 1 H, 1-H), 5.50
(vt, 4Ј-H), 5.43 (vt, 1 H, 3-H), 5.36 (d, 1 H, 4ЈЈ-H), 5.13 (dd, 1 H,
2ЈЈ-H), 5.07 (vt, 1 H, 4-H), 5.04 (dd, 1 H, 3ЈЈ-H), 4.95 (dd, 1 H, 2-
H), 4.60 (d, 1 H, 1ЈЈ-H), 4.35 (d, 1 H, 1Ј-Ha), 4.32 (d, 1 H, 3Ј-H),
4.27–4.29 (m, 2 H, 5-H, 6-Ha), 4.04–4.19 (m, 7 H, 6-Ha, 1Ј-Ha, 5Ј-
H, 6Ј-Ha, 6Ј-Hb, 6ЈЈ-Ha, 6ЈЈ-Hb), 3.92 (vt, 1 H, 5ЈЈ-H), 2.19, 2.15,
2.11, 2.11, 2.10, 2.09, 2.08, 2.05, 2.05, 2.00, 1.98 (11 s, 11 ϫ 3 H,
2,3,4,6-Tetra-O-acetyl-β-D-galactopyranosyl-(1Ǟ6)-2,3,4-tri-O-ace-
tyl-α- -glucopyranosyl 2,3,4,6-Tetra-O-acetyl-α-
D
D
-glucopyranoside
1
(11): H NMR (400 MHz, CDCl3): δ = 5.48 (vt, 1 H, 3Ј-H), 5.46
(vt, 1 H, 3-H), 5.41 (dd, 1 H, 4-H), 5.27 (d, 1 H, 1Ј-H), 5.23 (d, 1
H, 1-H), 5.15 (m, 1 H, 2-H), 5.12 (dd, 1 H, 2ЈЈ-H), 5.04 (m, 1 H,
3-H), 5.02 (vt, 1 H, 4-H), 4.96 (m, 1 H, 4Ј-H), 4.94 (m, 1 H, 2Ј-H),
4.73 (d, 1 H, 1ЈЈ-H), 4.18 (m, 1 H, 5-H), 4.11 (m, 1 H, 5Ј-H), 4.06
(m, 2 H, 6-Ha, 6-Hb), 4.03 (m, 3 H, 5ЈЈ-H, 6ЈЈ-Ha, 6ЈЈ-Hb), 3.92
(dd, 1 H, 6Ј-Hb), 3.44 (dd, 1 H, 6Ј-Ha), 2.11–1.98 (m, 33 H, CH3)
11 CH3) ppm; J1,2 = 3.8, J2,3 = 9.7, J3,4 = 9.8, J4,5 = 9.8, J1Јa,1Јb
11.0, J3Ј,4Ј = 7.9, J4Ј,5Ј = 7.5, J1ЈЈ,2ЈЈ = 7.8, J2ЈЈ,3ЈЈ = 10.5, J3ЈЈ,4ЈЈ
=
=
2.8, J4ЈЈ,5ЈЈ Ͻ 1, J5ЈЈ,6ЈЈa = 6.6, J5ЈЈ,6ЈЈb = 6.6 Hz. 13C NMR
(100 MHz, CDCl3): δ = 103.32 (C-2Ј), 102.24 (C-1ЈЈ), 89.85 (C-1),
82.75 (C-3Ј), 79.01 (C-5), 74.23 (C-4Ј), 71.18 (C-3ЈЈ), 71.16 (C-5ЈЈ),
70.57 (C-3), 70.52 (C-2), 69.00 (C-2ЈЈ), 68.58 (C-4), 68.47 (C-5),
67.00 (C-4ЈЈ), 64.27, 63.34, 62.22, 61.08 (C-6, C-1Ј, C-6Ј, C-6ЈЈ),
20.93–21.25 (m, CH3) ppm.
ppm; J1ЈЈ,2ЈЈ = 7.9, J2ЈЈ,3ЈЈ = 10.4, J3ЈЈ,4ЈЈ = 2.2, J1Ј,2Ј = 3.4, J2Ј,3Ј
=
9.9, J3Ј,4Ј = 9.9, J5Ј,6Јa = 6.3, J5Ј,6Јb = 1.9, J6Јa,6Јb = 10.4, J1,2 = 3.5,
J2,3 = 10.1, J3,4 = 9.9, J4,5 = 9.6 Hz. 13C NMR (100 MHz, CDCl3):
δ = 169.48–170.47 (C=O), 101.28 (C-1ЈЈ), 93.09 (C-1), 92.63 (C-1Ј),
71.14 (C-5ЈЈ), 70.47 (C-3), 70.46 (C-3Ј), 68.04 (C-6Ј), 67.31 (C-4ЈЈ),
62.47 (C-6ЈЈ), 62.28 (C-6), 21.16–20.92 (m, CH3) ppm. Further sig-
nals of a mixture of 9 and 11: 13C NMR (100 MHz, CDCl3): δ =
72.41, 71.50, 70.89, 70.80, 70.46, 70.18, 69.68, 69.48, 69.32, 69.22,
68.98 (2 C), 68.90, 68.84, 68.69, 68.54 ppm.
2,3,4,6-Tetra-O-acetyl-β-
O-acetyl-α-
D-galactopyranosyl-(1Ǟ6Ј)-2,3,4,6-tetra-
D
-glucopyranosyl 1,3,4-Tri-O-acetyl-β-D-fructofurano-
side (20): 1H NMR (400 MHz, CDCl3): δ = 5.59 (d, 1 H, 1-H), 5.48
2,3,4,6-Tetra-O-acetyl-β-
tyl-α- -glucopyranosyl 1,3,4,6-Tetra-O-acetyl-β-
(13): 1H NMR (400 MHz, CDCl3): δ = 5.62 (d, 1 H, 3Ј-H), 5.53
(d, 1 H, 1-H), 5.43 (vt, 1 H, 4Ј-H), 5.38–5.34 (m, 2 H, 3-H, 4ЈЈ-H), H, 5-H, 6-Ha, 6-Hb), 4.20–4.05 (m, 5 H, 1Ј-Ha, 1Ј-Hb, 5Ј-H, 6ЈЈ-
5.27 (dd, 1 H, 2ЈЈ-H), 4.93–4.96 (m, 2 H, 4-H, 3ЈЈ-H), 4.55 (d, 1 H, Ha, 6ЈЈ-Hb), 4.06 (m, 1 H, 6Ј-Hb), 3.97 (vt, 1 H, 5ЈЈ-H), 3.81 (dd,
1ЈЈ-H), 4.04–4.40 (m, 8 H, 5-H, 6-Ha, 6-Hb, 1Ј-Ha, 1Ј-Hb, 5Ј-H, 1 H, 6Ј-Ha), 2.15, 2.14, 2.11, 2.10, 2.10, 2.08, 2.06, 2.03, 2.03, 2.01,
6Ј-Ha, 6Ј-Hb), 3.81 (dd, 1 H, 2-H), 2.17, 2.14, 2.13, 2.11, 2.10, 2.07, 1.97 (11 s, 11 ϫ 3 H, 11 CH3) ppm; J1,2 = 3.8, J2,3 = 10.4, J3,4
2.07, 2.06, 2.05, 1.96, 1.96 (11 s, 11 ϫ 3 H, 11 CH3) ppm; J1,2 9.7, J4,5 = 10.1, J3Ј,4Ј = 7.3, J4Ј,5Ј = 7.0, J1ЈЈ,2ЈЈ = 7.9, J2ЈЈ,3ЈЈ = 10.5,
3.5, J2,3 = 9.8, J3Ј,4Ј = 7.9, J4Ј,5Ј = 7.3, J1ЈЈ,2ЈЈ = 7.8, J2ЈЈ,3ЈЈ = 10.6 Hz. J3ЈЈ,4ЈЈ = 3.5, J4ЈЈ,5ЈЈ Ͻ 1, J5ЈЈ,6ЈЈa = 7.3, J5ЈЈ,6ЈЈb = 7.3 Hz. 13C NMR
13C NMR (100 MHz, CDCl3): δ = 171.11, 171.00, 170.83, 170.70,
(100 MHz, CDCl3): δ = 171.10, 170.74, 170.70, 170.62, 170.53,
170.55, 170.49, 170.47, 170.19, 170.12, 169.97, 169.21 (11 C=O), 170.53, 170.46, 170.40, 170.30, 169.99, 169.93 (11 C=O), 103.90 (C-
D-galactopyranosyl-(1Ǟ2)-3,4,6-tri-O-ace-
(d, 1 H, 3Ј-H), 5.45 (vt, 1 H, 3-H), 5.39 (d, 1 H, 4ЈЈ-H), 5.30 (vt, 1
D
D-fructofuranoside H, 3Ј-H), 5.17 (dd, 1 H, 2ЈЈ-H), 5.07 (vt, 1 H, 4-H), 5.05 (dd, 1 H,
3ЈЈ-H), 4.89 (dd, 1 H, 2-H), 4.60 (d, 1 H, 1ЈЈ-H), 4.38–4.25 (m, 3
=
=
5512
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Eur. J. Org. Chem. 2007, 5506–5513