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sulted in a 87 % yield. H NMR (400 MHz, CDCl3): δ = 8.02–7.98 (m,
Methyl 2,3,4,6-Tetra-O-acetyl-ꢀ-
D
-glucopyranosyl-(1→6)-2,3,4-
2 H), 7.94–7.88 (m, 4 H), 7.88–7.81 (m, 2 H), 7.56–7.01 (m, 27 H),
5.91 (t, J = 9.6 Hz, 1 H), 5.70 (t, J = 9.7 Hz, 1 H), 5.62 (dd, J = 9.7,
7.8 Hz, 1 H), 4.91 (d, J = 10.9 Hz, 1 H), 4.84 (d, J = 7.8 Hz, 1 H), 4.75
(d, J = 11.5 Hz, 1 H), 4.69 (d, J = 11.5 Hz, 1 H), 4.63 (dd, J = 12.0,
3.4 Hz, 1 H), 4.61 (d, J = 12.1 Hz, 1 H), 4.58–4.48 (m, 3 H), 4.31 (d,
J = 11.2 Hz, 1 H), 4.17 (d, J = 9.1 Hz, 1 H), 4.12 (ddd, J = 13.4, 5.9,
3.3 Hz, 1 H), 3.90 (t, J = 9.3 Hz, 1 H), 3.80–3.69 (m, 2 H), 3.45 (dd,
tri-O-benzyl-α-D-glucopyranoside (14): General glycosylation pro-
cedure with CSA (0.2 equiv.) and a reaction time of 2 h. Purification
by flash column chromatography (toluene/acetone, 97:3) resulted
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in a 56 % yield. H NMR (400 MHz, CDCl3): δ = 7.38–7.23 (m, 15 H),
5.17 (t, J = 9.4 Hz, 1 H), 5.11–4.95 (m, 3 H), 4.86 (d, J = 10.9 Hz, 1
H), 4.82–4.76 (m, 2 H), 4.65 (d, J = 12.1 Hz, 1 H), 4.58–4.50 (m, 3 H),
4.23 (dd, J = 12.3, 4.6 Hz, 1 H), 4.11 (d, J = 12.2 Hz, 1 H), 4.06 (d, J =
J = 9.7, 3.5 Hz, 1 H), 3.40 (t, J = 9.3 Hz, 1 H), 3.23 (s, 3 H) ppm. 13C 10.5 Hz, 1 H), 3.97 (t, J = 9.2 Hz, 1 H), 3.76 (dd, J = 10.0, 4.1 Hz, 1
NMR (101 MHz, CDCl3): δ = 166.2, 165.9, 165.2, 165.0, 138.8, 138.3,
138.2, 133.5, 133.3, 133.2 (2 C), 129.9–127.5, 101.4, 98.0, 81.9, 79.8,
77.4, 75.6, 74.8, 73.4, 72.9, 72.2, 71.9, 69.8, 69.5, 68.4, 63.3, 55.1 ppm.
NMR spectroscopic data are in accordance with literature values.[22]
H), 3.72–3.62 (m, 2 H), 3.51 (dd, J = 9.6, 3.5 Hz, 1 H), 3.42 (t, J =
9.4 Hz, 1 H), 3.36 (s, 3 H), 2.04 (s, 3 H), 2.02 (s, 3 H), 1.99 (s, 3 H),
1.95 (s, 3 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 170.7, 170.4, 169.4,
169.1, 138.7, 138.1 (2 C), 128.6–127.6, 100.7, 98.1, 82.0, 79.8, 77.7,
75.8, 75.0, 73.4, 73.0, 71.8, 71.3, 69.7, 68.4, 68.2, 62.0, 55.2, 20.7 (2
C), 20.6 (2 C) ppm. NMR spectroscopic data are in accordance with
literature values.[26]
Methyl
2,3,4-tri-O-benzyl-α-
2,3,4,6-Tetra-O-benzoyl-α-
D
-mannopyranosyl-(1→6)-
D
-glucopyranoside (11): General glycosyl-
ation procedure with CSA (0.2 equiv.) and a reaction time of 2 h.
Purification by flash column chromatography (toluene/acetone,
Methyl
2,3,4,6-Tetra-O-benzyl-
D
-glucopyranosyl-(1→6)-2,3,4-
1
97:3) resulted in a 76 % yield. H NMR (400 MHz, CDCl3): δ = 8.12–
tri-O-benzyl-α-
D
-glucopyranoside (15): General glycosylation pro-
7.99 (m, 4 H), 7.94–7.87 (m, 2 H), 7.85–7.79 (m, 2 H), 7.65–7.13 (m,
27 H), 6.07 (t, J = 10.1 Hz, 1 H), 5.88 (dd, J = 10.1, 3.3 Hz, 1 H), 5.73
(dd, J = 3.3, 1.8 Hz, 1 H), 5.16 (d, J = 1.7 Hz, 1 H), 5.02 (d, J = 11.1 Hz,
1 H), 5.00 (d, J = 11.1 Hz, 1 H), 4.84 (d, J = 11.0 Hz, 1 H), 4.80 (d, J =
12.0 Hz, 1 H), 4.71–4.60 (m, 4 H), 4.41 (ddd, J = 9.9, 4.3, 2.3 Hz, 1
H), 4.34 (dd, J = 12.0, 4.4 Hz, 1 H), 4.04 (t, J = 9.3 Hz, 1 H), 3.94 (dd,
J = 10.9, 5.1 Hz, 1 H), 3.86 (dd, J = 10.1, 5.1 Hz, 1 H), 3.81 (dd, J =
11.0, 1.5 Hz, 1 H), 3.58 (dd, J = 9.6, 3.6 Hz, 1 H), 3.56–3.49 (m, 1 H),
3.45 (s, 3 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 166.2, 165.5 (2
C), 165.4, 138.8, 138.3 (2 C), 133.5 (2 C), 133.3, 133.2, 130.0–127.7,
98.0, 97.9, 82.2, 80.3, 77.8, 75.8, 75.1, 73.6, 70.4, 70.1, 70.0, 69.0, 67.0,
66.8, 62.8, 55.3 ppm. NMR spectroscopic data are in accordance
with literature values.[23]
cedure with CSA (0.1 equiv.) and a reaction time of 2 h. Purification
by flash column chromatography (EtOAc/hexane/toluene, 1:4:4) re-
sulted in an α/ꢀ (1:3) mixture in a 61 % yield. HSQC (400 MHz,
CDCl3): α-anomer: δ = 4.98/97.35 and 4.54/98.08 ppm; ꢀ-anomer:
δ = 4.60/98.16 and 4.35/103.93 ppm. 1H NMR (400 MHz, CDCl3):
mixture: δ = 7.35–7.09 (m, 46.66 H), 4.99–4.95 (m, 2.66 H), 4.91–4.89
(m, 1.33 H), 4.84–4.48 (m, 16 H), 4.45 (d, J = 11.0 Hz, 0.33 H), 4.41
(d, J = 12.1 Hz, 0.33 H), 4.34 (d, J = 7.8 Hz, 1 H), 4.18 (dd, J = 10.8,
1.9 Hz, 1 H), 3.99 (t, J = 9.3 Hz, 1 H), 3.97 (d, J = 9.3 Hz, 0.33 H),
3.85–3.38 (m, 13.33 H), 3.34 (s, 1 H), 3.32 (s, 3 H) ppm. 13C NMR
(101 MHz, CDCl3): mixture: δ = 139.0 (2 C), 138.9, 138.6 (2 C), 138.5
(3 C), 138.4, 138.3 (2 C), 138.2, 138.1, 128.6–127.6, 103.9, 98.1, 98.2,
97.4, 84.9, 82.3, 82.2, 82.1, 81.8, 80.3, 80.1, 79.9, 78.1, 78.0, 77.9, 77.7,
75.8 (3 C), 75.6, 75.1 (2 C), 75.0 (3 C), 73.6, 73.5 (3 C), 72.5, 70.5,
70.4, 70.0, 69.1, 68.7, 68.6, 66.2, 55.3 (2 C) ppm. NMR spectroscopic
data are in accordance with literature values.[26]
Methyl
2,3,4-tri-O-benzyl-α-
2,3,4,6-Tetra-O-benzoyl-ꢀ-
D
-galactopyranosyl-(1→6)-
D
-glucopyranoside (12): General glycosyl-
ation procedure with CSA (0.2 equiv.) and a reaction time of 2 h.
Purification by flash column chromatography (toluene/acetone,
97:3) resulted in a 73 % yield. 1H NMR (400 MHz, CDCl3): δ = 8.10
(d, J = 7.6 Hz, 2 H), 8.03 (d, J = 7.6 Hz, 2 H), 7.90 (d, J = 7.7 Hz, 2
H), 7.78 (d, J = 7.7 Hz, 2 H), 7.70–6.99 (m, 27 H), 5.99 (br. s, 1 H),
5.86 (t, J = 9.1 Hz, 1 H), 5.61 (d, J = 10.4 Hz, 1 H), 4.91 (d, J = 10.9 Hz,
1 H), 4.79–4.65 (m, 4 H), 4.64–4.54 (m, 2 H), 4.52 (d, J = 3.5 Hz, 1 H),
4.46–4.34 (m, 2 H), 4.30–4.17 (m, 2 H), 3.92 (t, J = 9.2 Hz, 1 H), 3.81–
3.68 (m, 2 H), 3.44–3.32 (m, 2 H), 3.22 (s, 3 H) ppm. 13C NMR
(101 MHz, CDCl3): δ = 166.1, 165.7 (2 C), 165.2, 138.9, 138.3, 138.2,
133.7, 133.4 (2 C), 133.2, 130.1–127.6, 102.1, 98.0, 82.0, 79.9, 77.6,
75.6, 74.8, 73.4, 71.7, 71.5, 69.8, 69.7, 68.8, 68.2, 62.0, 55.1 ppm. NMR
spectroscopic data are in accordance with literature values.[24]
Methyl
2,3,6-tri-O-benzyl-α-
2,3,4,6-Tetra-O-benzoyl-ꢀ-
D
-glucopyranosyl-(1→4)-
D
-glucopyranoside (20): General glycosyl-
ation procedure with CSA (0.2 equiv.) and a reaction time of 3–24 h.
Purification by flash column chromatography (toluene/hexane/
EtOAc, 4:4:1) resulted in a 27–40 % yield (corrected for small impuri-
1
ties, which could not be removed). H NMR (400 MHz, CDCl3): δ =
8.00–7.80 (m, 8 H), 7.61–7.03 (m, 27 H), 5.61 (d, J = 9.5 Hz, 1 H),
5.55 (t, J = 9.6 Hz, 1 H), 5.47 (dd, J = 9.5, 8.0 Hz, 1 H), 5.07 (d, J =
11.2 Hz, 1 H), 4.85–4.71 (m, 4 H), 4.70–4.37 (m, 3 H), 4.34 (d, J =
12.1 Hz, 1 H), 4.31–4.22 (m, 1 H), 3.97 (t, J = 9.4 Hz, 1 H), 3.88 (t, J =
9.2 Hz, 1 H), 3.75–3.67 (m, 2 H), 3.57–3.34 (m, 3 H), 3.28 (s, 3 H)
ppm. 13C NMR (101 MHz, CDCl3): δ = 166.1, 165.8, 165.1, 164.8,
139.3, 138.4, 137.9, 133.4, 133.3, 133.2, 133.0, 129.9–127.2, 100.4,
98.5, 80.0, 78.8, 77.3, 75.4, 73.64, 73.6, 73.2, 72.3, 71.8, 69.9, 69.5,
67.6, 63.2, 55.4 ppm. NMR spectroscopic data are in accordance
with literature values.[22]
Methyl 3,4,6-Tri-O-benzoyl-2-deoxy-2-phthalimido-ꢀ-
D-gluco-
pyranosyl-(1→6)-2,3,4-tri-O-benzyl-α- -glucopyranoside (13):
D
General glycosylation procedure with CSA (0.1 equiv.) and a 1 h
reaction time. Purification by flash column chromatography (EtOAc/
1
hexane/toluene, 1:3:3) resulted in a 77 % yield. H NMR (400 MHz,
CDCl3): δ = 8.00 (dd, J = 8.3, 1.2 Hz, 2 H), 7.89 (dd, J = 8.3, 1.2 Hz,
2 H), 7.82–7.71 (m, 2 H), 7.63–7.16 (m, 26 H), 7.02 (dd, J = 6.6, 2.9 Hz,
2 H), 6.28 (dd, J = 10.7, 9.3 Hz, 1 H), 5.69 (t, J = 9.6 Hz, 1 H), 5.64
(d, J = 8.5 Hz, 1 H), 4.85 (d, J = 10.9 Hz, 1 H), 4.73–4.52 (m, 6 H),
4.43–4.38 (m, 2 H), 4.30–4.21 (m, 1 H), 4.15–4.11 (m, 2 H), 3.84 (t,
J = 9.3 Hz, 1 H), 3.72 (dd, J = 10.3, 4.7 Hz, 1 H), 3.68 (dd, J = 10.3,
3.8 Hz, 1 H), 3.39 (dd, J = 9.7, 3.5 Hz, 1 H), 3.26 (t, J = 9.4 Hz, 1 H),
3.15 (s, 3 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 167.0 (2 C), 166.3,
165.8, 165.3, 138.8, 138.6, 137.9, 134.2 (2 C), 133.5, 133.4, 133.2,
Methyl
2,3,6-tri-O-benzoyl-α-
2,3,4,6-Tetra-O-benzoyl-ꢀ-
D
-glucopyranosyl-(1→4)-
D
-galactopyranoside (21): General glyc-
osylation procedure with TfOH (0.3 equiv.) and a reaction time of
24 h. Purification by DCVC (0–70 % EtOAc in hexane) resulted in a
white solid in a 81 % yield. 1H NMR (400 MHz, CDCl3): δ = 8.05–7.92
(m, 8 H), 7.88–7.77 (m, 6 H), 7.61–7.24 (m, 19 H), 7.13 (t, J = 7.8 Hz,
2 H), 5.87–5.81 (m, 2 H, 3-H, 3′-H), 5.71–5.62 (m, 2 H, 2′-H, 4′-H),
5.26 (dd, J = 10.7, 3.6 Hz, 1 H, 2-H), 5.20 (d, J = 3.6 Hz, 1 H, 1-H),
5.09 (d, J = 7.8 Hz, 1 H, 1′-H), 4.73 (dd, J = 11.7, 4.7 Hz, 1 H, 6-Ha),
130.0–123.6, 98.7, 98.0, 82.0, 79.8, 77.8, 75.8, 74.9, 73.5, 72.3, 71.2, 4.58–4.52 (m, 2 H, 4-H, 6-Hb), 4.47 (dd, J = 12.2, 3.3 Hz, 1 H, 6-Ha′),
70.5, 69.3, 68.9, 63.5, 55.1, 54.9 ppm. NMR spectroscopic data are
4.42–4.34 (m, 2 H, 6-Hb′), 3.96 (dt, J = 9.8, 3.9 Hz, 1 H, 5′-H), 3.34 (s,
in accordance with literature values.[25]
3 H, OMe) ppm. 13C NMR (101 MHz, CDCl3): δ = 166.1, 166.1, 166.0
Eur. J. Org. Chem. 0000, 0–0
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