Chemical Papers
Scheme 1 General synthetic route of glucosyl esters
(
500 MHz, DMSO): δ/ppm 8.22 (d, 1H, J = 6.0 Hz, NH),
.14 (s, 1H, C –OH), 4.89 (s, 1H, C –OH), 4.79 (s, 1H,
α-d-glucopyranoside (1 mmol) to give oily product 11′
1
5
(0.57 mmol, 0.26 g, 57.3% yield); H NMR (500 MHz,
4
3
C –OH), 4.46 (s, 1H, H-1), 4.34 (d, 1H, J=11.5 Hz, H-6b),
DMSO): δ/ppm 8.10 (d, 1H, J=8.0 Hz, NH), 5.12 (s, 1H,
OH), 4.88 (s, 1H, OH), 4.77 (s, 1H, OH), 4.49 (d, 1H,
J=3.0 Hz, H-1), 4.40–4.38 (m, 1H, H-6b), 4.27–4.23 (m,
1H, H-5), 4.02–3.93 (m, 1H, CH), 3.53–3.51 (m, 1H, H-6a),
2
4
.21–4.19 (m, 1H, H-5), 4.02–3.89 (m, 1H, CH), 3.54–3.51
(
m, 1H, H-6a), 3.34–3.31 (m, 1H, H-2), 3.24 (s, 3H, OCH ),
3
3
2
.20–3.16 (m, 1H, H-3), 3.01–2.97 (m, 1H, H-4), 2.02 (t,
H, J=7.0 Hz, CH ), 1.41–1.39 (m, 2H, CH ), 1.21–1.19
3.36–3.34 (m, 1H, H-2), 3.23 (s, 3H, OCH ), 3.17–3.15 (m,
2
2
3
(
m, 3H, CH ), 1.18 (s, 20H, 10 × (CH )), 0.84–0.86 (m,
1H, H-3), 3.04–3.00 (m, 1H, H-4), 2.07–2.03 (m, 2H, CH ),
3
2
2
1
3
3
H, CH ); C NMR (125 MHz, DMSO): δ/ppm 173.24
1.60–1.56 (m, 1H, CH), 1.51–1.44 (m, 2H, CH ), 1.44–1.42
3
2
(
NHC=O), 169.54 (C=O), 95.22, 78.41, 76.68, 72.93, 69.82,
(m, 2H, CH ), 1.23–1.21 (m, 12H, 6 × (CH )), 0.85–0.78
2
2
1
3
6
2
0.83, 35.56, 31.75, 29.51, 29.52, 29.42, 29.29, 29.17,
(m, 9H, CH , 2 × CH ); C NMR(125 MHz, DMSO): δ/
3 3
9.06, 25.65, 22.56, 14.41; ESI–MS: C H N O , m/z: 484
ppm 173.43 (NHC=O), 171.13 (C=O), 97.15 (C-1), 79.42
(C-5), 76.73 (C-3), 73.77 (C-2), 70.38 (C-4), 61.79 (C-6),
56.67, 46.22, 36.36, 34.47, 33.71, 31.89, 29.62, 29.33,
29.22, 28.79, 28.41, 28.26, 25.62, 24.74, 22.69, 22.32,
2
4
46
2
7
+
[
M+Na] .
Methyl 6-O-(N-palmitoyl-glycyl)-d-glucosyl ester
14): treatment of 10 (0.49 g, 1.5 mmol) and methyl
(
+
α-d-glucopyranoside (1 mmol) to give oily product 14
17.26, 14.18; ESI–MS: C H N O , m/z: 470 [M+Na] .
2
3
444
2
7
1
(
0.66 mmol, 0.30 g, 65.8% yield); H NMR (500 MHz,
Methyl 6-O-(N-dodecanoyl-valine acyl)-d-glucosyl
ester (12′): treatment of 8′ (1.5 mmol, 0.47 g) and methyl
α-d-glucopyranoside (1 mmol) to give oily product 12′
DMSO): δ/ppm 8.23 (t, 1H, J= 6.0 Hz, NH), 5.36 (s, 1H,
OH), 5.28 (s, 1H, OH), 5.11 (s, 1H, C –OH), 5.02 (m, 1H,
2
1
H-1), 4.62 (s, 1H, CH), 4.28–4.25 (m, 1H, CH), 4.10–4.07
(0.8 mmol, 0.38 g, 79.3% yield); H NMR (500 MHz,
(
m, 1H, CH), 3.55–3.53 (m, 1H, CH), 3.52–3.47 (m, 1H,
DMSO): δ/ppm 8.08 (d, 1H, J = 7.5 Hz, NH), 5.11 (s,
CH), 3.26 (s, 3H, OCH ), 3.23–3.20 (m, 1H, H-3), 3.09–3.07
1H, C –OH), 4.86 (s, 1H, C –OH), 4.76 (s, 1H, C –OH),
3
4
3
2
(
m, 1H, CH), 2.11–2.09 (m, 2H, CH ), 1.49–1.47 (m, 2H,
4.47 (d, 1H, J = 3.0 Hz, H-1), 4.40–4.37 (m, 1H, H-6b),
2
CH ), 1.27–1.26 (m, 3H, CH ), 1.24 (s, 24H, 12 ×(CH )),
4.28–3.49 (m, 1H, H-6a), 3.35–3.33 (m, 1H, H-2), 3.22 (s,
2
3
2
1
3
0
.88–0.86 (m, 3H, CH ); C NMR (125 MHz, DMSO): δ/
3H, OCH ), 3.16–3.14 (m, 1H, H-3), 3.04–3.01 (m, 1H,
3
3
ppm 173.24 (NHC=O), 169.54 (C=O), 95.25 (C-1), 78.42
H-4), 2.08–2.04 (m, 2H, CH ), 1.61–1.55 (m, 1H, CH),
2
(
C-5), 76.71 (C-3), 72.93 (C-2), 69.82 (C-4), 60.90 (C-6),
1.52–1.46 (m, 2H, CH ), 1.44–1.42 (m, 2H, CH ), 1.22–1.19
2
2
3
5.56, 31.76, 29.52, 29.47, 29.42, 29.29, 29.17, 29.06, 25.65,
(m, 16H, 8×(CH )), 0.84–0.83 (m, 3H, CH ), 0.82–0.80 (m,
2
3
+
13
2
2.56, 14.41; ESI–MS: C H N O , m/z: 512 [M+Na] .
3H, CH ). 0.79–0.77 (m, 3H, CH ); C NMR (125 MHz,
3 3
2
6
50
2
7
Methyl 6-O-(N-decanoy l-valine acyl)-d-glucosyl
DMSO): δ/ppm 173.90 (NHC=O), 171.10, 95.14 (C-1),
ester (11′): treatment of 7′ (1.5 mmol, 0.43 g) and methyl
76.69 (C-5), 72.80 (C-3), 69.77 (C-2), 60.83 (C-4), 56.60
1
3