ChemBioChem
10.1002/cbic.201700247
FULL PAPER
13C NMR (D
O, 100 MHz): δ 106.8, 106.6, 106.5, 99.9, 99.5, 99.4, (D
O, 400 MHz): δ 5.16 (s, 2 H), 5.03 (s, 1 H), 4.91 (s, 4 H), 4.13-
2
2
8
7
2
2.5, 82.2, 81.9, 81.5, 78.0, 76.8, 76.5, 72.8, 71.4, 71.2, 70.9, 3.56 (m, 56 H), 1.57 (br s, 4 H), 1.31 (br s, 52 H), 0.89 (s, 6 H);
0.7, 70.3, 70.1, 70.0, 66.8, 66.6, 65.5, 61.1, 32.1, 30.3, 30.1, 13C NMR (D
O, 100 MHz): 107.8, 106.9, 106.6, 100.0, 99.9, 99.5,
2
9.7, 26.4, 26.3, 22.7, 13.9; ESI-MS Calcd. for C78
Na] : 1695.9284, found 1695.9067.
H
144
O
37Na [M 99.4, 81.8, 81.6, 81.3, 78.0, 76.8, 76.6, 72.7, 71.4, 71.1, 70.7,
+
+
70.2, 70.1, 69.9, 66.8, 66.6, 65.6, 61.6, 61.0, 32.1, 30.3, 30.0,
2
C
9.8, 29.7, 26.4, 26.3, 22.7, 13.9; ESI-MS Calcd. for
+
8-O-Hexadecyl-3,6,10-trioxa-1,8-hexacosanedioyl 2,3,4,6-
78
H
144
O37Na [M + Na] : 1695.9284, found 1695.9478.
tetra-O-acetyl-α-D-mannopyranosyl-(1→6)-2,3,4-tri-O-benzoyl-α-
D-mannopyranosyl-(1→5)-2,3-di-O-benzoyl-α-D-
arabinofuranosyl-(1→5)-[2,3,4,6-tetra-O-acetyl-α-D-
Methyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl-(1→6)-
2,3,4-tri-O-benzoyl-α-D-mannopyranosyl-(1→5)-2,3-di-O-
mannopyranosyl-(1→6)-2,3,4-tri-O-benzoyl-α-D-mannopyranosyl- benzoyl-α-D-arabinofuranosyl-(1→2)-[2,3,4,6-tetra-O-acetyl-α-D-
1→5)-2,3-di-O-benzoyl-α-D-arabinofuranosyl-(1→2)]-3-O- mannopyranosyl-(1→6)-2,3,4-tri-O-benzoyl-α-D-mannopyranosyl-
benzoyl-α-D-arabinofuranoside (15): A solution of 11 (0.44 g, (1→5)-2,3-di-O-benzoyl-α-D-arabinofuranosyl-(1→3)]-5-O-acetyl-
.35 mmol), 14 (0.1 g, 0.12 mmol) and MS 4 Å (0.6 g) in α-D-arabinofuranoside (17): A solution of 11 (0.55 g, 0.44 mmol),
dichloromethane (5 mL) was stirred for 10 min., N- 16 (0.03 g, 0.146 mmol) and MS 4 Å (0.6 g) in dichloromethane
iodosuccinimide (0.11 g, 0.50 mmol) and silver (5 mL) was stirred for 10 min., N-iodosuccinimide (0.12 g, 0.53
trifluoromethanesulfonate (0.035 g, 0.14 mmol) were added into it mmol) and silver trifluoromethanesulfonate (0.045 g, 0.18 mmol)
(
0
o
o
at 0 C, under N
at the same temperature for another 30 min., neutralized with mixture was stirred at the same temperature for another 30 min.,
Et N, filtered and filtrate diluted with dichloromethane (50 mL), neutralized with Et N, filtered and filtrate diluted with
washed with satd. aq. sodium thiosulphate (2 x 20 mL) and water dichloromethane (50 mL), washed with satd. aq. sodium
1 x 20 mL). The organic portion was dried (Na SO ), filtered and thiosulphate (2 x 20 mL) and water (1 x 20 mL). The organic
2 2
atmosphere. The reaction mixture was stirred were added into it at 0 C, under N atmosphere. The reaction
3
3
(
2
4
filtrate concentrated in vacuo and purified (pet. ether/EtOAc = portion was dried (Na
2
SO
4
), filtered and filtrate concentrated in
1
7
:3) to afford 15, as a gum. Yield: 0.19 g (51%); H NMR (CDCl
3
,
vacuo and purified (pet. ether/EtOAc = 1:1) to afford 17, as a gum.
1
400 MHz): δ 8.14 (d, J = 7.2 Hz, 4 H), 8.11-8.09 (m, 3 H), 8.05 (d, Yield: 0.203 g (56%); H NMR (CDCl
3
, 400 MHz): δ 8.13 (d, J =
J = 8 Hz, 4 H), 8.01 (d, J = 8 Hz, 2 H), 7.94 (d, J = 7.2 Hz, 4 H), 7.2 Hz, 4 H), 8.08 (dd, J = 2.8 Hz, 7.6 Hz, 4 H), 8.04-8.01 (m, 3
7.75 (d, J = 7.6 Hz, 4 H), 7.62-7.28 (m, 31 H), 7.23 (d, J = 7.6 Hz, H), 7.96 (d, J = 7.6 Hz, 4 H), 7.75 (d, J = 7.6 Hz, 4 H), 7.62-7.39
3 H), 6.05-5.99 (m, 2 H), 5.90 (d, J = 10.4 Hz, 2 H), 5.84 (s, 2 H), (m, 17 H), 7.36-7.22 (m, 14 H), 5.98 (t, J = 10 Hz, 2 H), 5.93-5.88
5.74 (d, J = 4.4 Hz, 3 H), 5.68 (d, J = 5.6 Hz, 1 H), 5.66 (s, 1 H), (m, 2 H), 5.82 (s, 2 H), 5.72 (d, J = 5.2 Hz, 2 H), 5.61 (d, J = 4.8
5.51 (s, 1 H), 5.46-5.43 (m, 3 H), 5.38-5.36 (m, 2 H), 5.33 (s, 1 H), Hz, 3 H), 5.44 (dd, J = 3.2 Hz, 10 Hz, 2 H), 5.35 (d, J = 3.2 Hz, 2
5.29-5.24 (m, 2 H), 5.20 (s, 2 H), 4.88 (s, 2 H), 4.57-4.54 (m, 6 H), H), 5.25 (t, J = 10.2 Hz, 2 H), 5.18 (d, J = 8 Hz, 2 H), 5.12 (s, 1 H),
4.29-3.94 (m, 13 H), 3.82 (d, J = 12 Hz, 2 H), 3.68 (d, J = 11.2 Hz, 4.88 (s, 2 H), 4.54-4.49 (m, 5 H), 4.44 (dd, J = 5.2 Hz, 12.4 Hz, 1
5 H), 3.60-3.42 (m, 11 H), 2.07 (s, 3 H), 2.06 (s, 3 H), 2.04 (s, 6 H), 4.33-4.26 (m, 4 H), 4.15-3.95 (m, 10 H), 3.86 (d, J = 12 Hz, 2
H), 1.94 (s, 3 H), 1.93 (s, 3 H), 1.90 (s, 6 H), 1.54-1.51 (m, 4 H), H), 3.69 (d, J = 10.8 Hz, 2 H), 3.47 (s, 3 H), 2.07 (s, 3 H), 2.06 (s,
.24 (br s, 50 H), 0.88 (t, J = 6.8 Hz, 6 H); 13C NMR (CDCl , 100 3 H), 2.05 (s, 3 H), 2.04 (s, 9 H), 1.91 (s, 9 H); 13C NMR (CDCl
MHz): δ 170.4, 169.8, 169.7, 169.3, 165.9, 165.8, 165.7, 165.6, 100 MHz): δ 171.1, 170.7, 170.5, 169.8, 169.7, 169.3, 165.8,
1
3
3
,
1
1
1
1
8
7
6
2
65.5, 165.4, 165.3, 164.9, 139.2, 133.4, 133.2, 133.1, 133.0, 165.7, 165.6, 165.4, 165.3, 164.9, 133.4, 133.3, 133.2, 132.9,
32.9, 130.0, 129.9, 129.8, 129.7, 129.4, 129.3, 129.2, 129.1, 130.0, 129.9, 129.8, 129.7, 129.3, 129.2, 129.1, 129.0, 128.9,
29.0, 128.9, 128.8, 128.7, 128.5, 128.4, 128.3, 128.2, 128.1, 128.7, 128.5, 128.4, 128.1, 107.6, 106.1, 105.9, 98.2, 97.6, 97.5,
06.8, 106.0, 104.9, 98.3, 98.2, 97.7, 97.6, 84.1, 82.6, 82.2, 82.1, 87.1, 82.8, 82.4, 81.9, 79.3, 77.2, 70.3, 70.1, 69.5, 69.4, 69.0,
1.9, 81.5, 78.1, 77.9, 77.2, 71.6, 71.4, 71.0, 70.8, 70.6, 70.5, 68.6, 66.8, 66.1, 65.9, 62.2, 60.4, 55.3, 21.0, 20.8, 20.7, 20.5;
+
0.4, 70.3, 70.1, 69.5, 69.4, 69.3, 69.1, 68.6, 67.4, 66.8, 66.6, ESI-MS Calcd. for C128
6.1, 65.9, 62.2, 31.9, 31.6, 30.3, 30.1, 29.7, 29.6, 29.5, 29.3, 2517.7609.
H
126
O
52Na [M + Na] : 2517.7113, found
6.1, 26.0, 22.6, 20.7, 20.6, 20.5, 20.4, 14.1; MALDI-TOF-MS
+
Calcd. for C171
177.3050.
H
204
O
56Na [M+Na] : 3177.3047 (100%), found
Methyl α-D-mannopyranosyl-(1→6)-α-D-mannopyranosyl-
(1→5)-α-D-arabinofuranosyl-(1→2)-[α-D-mannopyranosyl-(1→6)-
α-D-mannopyranosyl-(1→5)-α-D-arabinofuranosyl-(1→3)]-α-D-
α-D- arabinofuranoside (3): Sodium methoxide in methanol (1 M)
(0.15 mL) was added to a solution of 17 (0.15 g, 0.06 mmol) in
methanol/tetrahydrofuran (1:1) (5 mL) at room temperature and
3
8
-O-Hexadecyl-3,6,10-trioxa-1,8-hexacosanedioyl
mannopyranosyl-(1→6)-α-D-mannopyranosyl-(1→5)-α-D-
arabinofuranosyl-(1→5)-[α-D-mannopyranosyl-(1→6)-α-D-
mannopyranosyl-(1→5)-α-D-arabinofuranosyl-(1→2)]-α-D-
+
stirred for 12 h, neutralized with Amberlite ion exchange (H )
arabinofuranoside (2): Sodium methoxide in methanol (1 M) resin, filtered and filtrate concentrated in vacuo to afford 3, as a
0.15 mL) was added to a solution of 15 (0.15 g, 0.048 mmol) in solid. Yield: 0.058 g, (90%); [] +91.98 (c 1, D
O); 1H NMR
OD, 400 MHz): δ 5.03 (s, 3 H), 4.96 (s, 1 H), 4.80 (d, J = 3.2
(
D
2
methanol/tetrahydrofuran (1:1) (5 mL) at room temperature and (CD
3
+
stirred for 12 h, neutralized with Amberlite ion exchange (H ) Hz, 3 H), 4.13-4.00 (m, 7 H), 3.87-3.64 (m, 32 H), 3.38 (s, 3 H);
1
3
resin, filtered and filtrate concentrated in vacuo to afford 2, as a
3
C NMR (CD OD, 100 MHz): 109.3, 108.8, 108.7, 101.6, 101.4,
solid. Yield: 0.073 g (92%); [] +22.82 (c 0.5, D
D
2
O); 1H NMR 101.1, 101.0, 87.6, 83.8, 83.7, 83.5, 83.2, 82.2, 79.1, 79.0, 74.3,
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