W. Peng et al. / Carbohydrate Research 340 (2005) 1682–1688
1687
3.11. 40-O-Methylquercetin-3-yl a-L-rhamnopyranosyl-
(1!2)-b-D-glucopyranoside (1)
156.7, 148.0, 145.4, 135.7, 135.6, 134.0, 133.6, 133.1,
132.8, 130.1, 129.9, 129.6, 129.3, 129.2, 129.0, 128.7,
128.5, 128.4, 128.2, 128.0, 127.8, 127.5, 123.7, 122.0,
115.3, 110.5, 106.0, 99.8, 98.7, 98.3, 93.1, 75.0, 71.8,
71.5, 71.0, 70.7, 70.4, 69.5, 68.2, 67.0, 61.7, 20.5, 20.4,
17.1; HRESIMS (m/z): Calcd for C73H63O22 (M++H):
1291.3806. Found 1291.3845.
A solution of 14 (104 mg, 0.086 mmol) in 1:1 EtOH–
EtOAc (4 mL) was treated with a catalytic amount of
10% Pd–C. After stirring under 1 atm of H2 at 40 °C
for 7 h, the reaction mixture was filtered through a pad
of Celite and concentrated in vacuo. The residue was dis-
solved in 2:3 CH2Cl2–CH3OH (15 mL), followed by
addition of a catalytic amount of CH3ONa. After stirring
for 4 h at room temperature, the mixture was neutralized
with Dowex 50-X8 (H+) resin. The resin was filtered off
and washed with CH3OH. The filtrate and washings were
combined and concentrated. The residue was purified by
3.13. 40,7-Di-O-benzyl-30-O-methylquercetin-3-yl 2,3,4-
tri-O-benzoyl-a-L-rhamnopyranosyl-(1!2)-4,6-di-O-acet-
yl-3-O-benzoyl-b-D-glucopyranoside (17) and 40,7-di-O-
benzyl-30,5-di-O-methylquercetin-3-yl 2,3,4-tri-O-benz-
oyl-a-L-rhamnopyranosyl-(1!2)-4,6-di-O-acetyl-3-O-
benzoyl-b-D-glucopyranoside (18)
silica gel column chromatography (2:1 toluene–CH3OH)
20
D
to give 1 (46 mg, 86%) as a yellow solid: ½aꢁ ꢀ94 (c 0.56,
A solution of 16 (50 mg, 0.039 mmol), K2CO3 (6 mg,
1.1 equiv), and MeI (2.4 lL, 1.0 equiv) in anhydrous
DMF (1.0 mL) was stirred at room temperature for
1 day under argon. The resulting mixture was diluted
with water, and extracted with EtOAc. The organic
layer, after being washed with 1 N HCl and water,
respectively, was dried over Na2SO4, and concentrated.
The residue was purified by silica gel column chroma-
tography (7:2 toluene–EtOAc) to afford the 30-O-methyl
17 (27 mg, 53%). 30,5-Di-O-methyl 18 (18 mg, 36%) was
isolated as yellow foams when 1.5 equiv of MeI was used
1
CH3OH); H NMR (DMSO-d6, 400 MHz): d 12.56 (s,
1H, 5-OH), 7.66 (dd, J 1.8, 8.8 Hz, 1H, H-60), 7.47 (d, J
1.8 Hz, 1H, H-20), 6.97 (d, J 8.8 Hz, 1H, H-50), 6.35 (d,
J 1.8 Hz, 1H, H-8), 6.13 (d, J1.8 Hz, 1H, H-6), 5.61 (d,
J 7.7 Hz, 1H, GlcH-1), 5.00 (br s, 1H, RhaH-1), 3.79 (s,
3H, OCH3), 0.68 (d, J 6.2 Hz, 3H); 13C NMR (DMSO-
d6, 100 MHz): d 177.3, 164.5, 161.2, 156.4, 155.7, 150.0,
146.0, 133.2, 122.7, 121.5, 115.5, 111.3, 103.9, 100.6,
98.8, 98.4, 93.6, 77.6, 77.4, 77.3, 71.8, 70.6, 70.2, 69.7,
68.3, 60.9, 55.7, 17.2; HRESIMS (m/z): Calcd for
C28H32O16Na (M++Na): 647.1583. Found 647.1570.
22
1
in the reaction. 17: ½aꢁ ꢀ20 (c 0.45, CHCl3); H NMR
D
(CDCl3, 300 MHz): d 12.71 (s, 1H, 5-OH), 8.07 (d, J
7.1 Hz, 2H), 7.92 (d, J = 7.1 Hz, 2H), 7.85 (d,
J = 6.9 Hz, 2H), 7.81 (d, J 7.1 Hz, 2H), 7.76 (d, J
1.9 Hz, 1H), 7.65 (dd, J 1.9, 8.5 Hz, 1H), 7.57 (t, J
7.4 Hz, 1H), 7.50–7.21 (m, 21H), 7.02 (d, J 8.5 Hz,
1H), 6.56 (d, J 2.2 Hz, 1H), 6.53 (d, J 2.2 Hz, 1H),
6.09 (dd, J 3.4, 10.0 Hz, 1H), 5.82 (d, J 7.7 Hz, 1H),
5.74 (t, J 9.3 Hz, 1H), 5.57 (t, J 9.9 Hz, 1H), 5.53 (m,
1H), 5.30–5.15 (m, 2H), 5.28 (s, 2H), 5.18 (s, 2H), 4.78
(m, 1H), 4.18–3.95 (m, 3H), 4.03 (s, 3H), 3.76 (m, 1H),
1.96 (s, 3H), 1.92 (s, 3H), 1.12 (d, J 6.3 Hz, 3H); 13C
NMR (CDCl3, 75 MHz): d 177.5, 170.3, 169.6, 165.8,
165.4, 165.1, 164.6, 162.2, 157.7, 156.8, 150.6, 148.9,
136.4, 135.7, 133.9, 133.1, 132.8, 130.0, 129.7, 129.4,
129.1, 128.8, 128.7, 128.3, 128.1, 127.4, 127.2, 123.1,
122.4, 112.7, 106.1, 100.1, 98.8, 98.4, 93.2, 77.7, 75.0,
71.8, 71.7, 70.7, 70.5, 69.5, 68.1, 67.1, 61.5, 56.2, 20.5,
20.4, 17.1; HRESIMS (m/z): Calcd for C74H65O22
3.12. 40,7-Di-O-benzylquercetin-3-yl 2,3,4-tri-O-benzoyl-
a-L-rhamnopyranosyl-(1!2)-4,6-di-O-acetyl-3-O-ben-
zoyl-b-D-glucopyranoside (16)
A mixture of 40,7-di-O-benzylquercetin 15 (96 mg,
0.2 mmol), TBAB (64 mg, 0.2 mmol), and K2CO3
(55 mg, 0.6 mmol) in 1:1 CHCl3–H2O (4 mL) was stirred
at 40 °C for 1 h. Then, the glycosyl bromide 13 (247 mg,
0.3 mmol) added, and stirring was continued at 40 °C
for 1 day. The reaction mixture was then diluted with
CH2Cl2, and washed with 1 N HCl, water, and brine,
respectively. The organic layer was dried over Na2SO4,
and concentrated in vacuo. The residue was purification
by silica gel column chromatography (2:1 toluene–
EtOAc) to afford 16 (157 mg, 61%) as a yellow foam:
22
D
½aꢁ
ꢀ18 (c 0.75, CHCl3); 1H NMR (CDCl3,
300 MHz): d 12.66 (s, 1H, 5-OH), 8.11 (d, J = 7.1 Hz,
1H), 8.04 (d, J 7.1 Hz, 2H), 7.90 (d, J 7.1 Hz, 2H),
7.82 (d, J 7.1 Hz, 2H), 7.78 (d, J 7.4 Hz, 2H), 7.69–
7.56 (m, 2H), 7.53–7.15 (m, 21H), 7.03 (d, J 8.5 Hz,
1H), 6.52 (d, J 2.2 Hz, 1H), 6.50 (d, J2.2 Hz, 1H), 6.05
(dd, J 3.4, 10.0 Hz, 1H), 5.76 (d, J 7.4 Hz, 1H), 5.69
(t, J 9.3 Hz, 1H), 5.54 (t, J 9.9 Hz, 1H), 5.50 (m, 1H),
5.25–5.15 (m, 2H), 5.21 (s, 2H), 5.15 (s, 2H), 4.74 (m,
1H), 4.18 (dd, J 7.7, 9.1 Hz, 1H), 4.11 (m, 2H), 3.76
(m, 1H), 1.93 (s, 3H), 1.92 (s, 3H), 1.12 (d, J 6.3 Hz,
3H); 13C NMR (CDCl3, 75 MHz): d 177.5, 170.6,
169.7, 165.7, 165.4, 165.1, 164.6, 164.5, 162.0, 157.5,
(M++H): 1305.3962. Found 1305.3984.
23
D
18: ½aꢁ ꢀ38 (c 0.93, CHCl3); 1H NMR (CDCl3,
300 MHz): d 8.03 (d, J 7.1 Hz, 2H), 7.93 (d, J 7.1 Hz,
2H), 7.80 (d, J 7.1 Hz, 2H), 7.76 (m, 3H), 7.60 (dd, J
1.9, 8.5 Hz, 1H), 7.53 (t, J 7.4 Hz, 1H), 7.49–7.24 (m,
20H), 7.19 (t, J 7.7 Hz, 1H), 6.98 (d, J 8.8 Hz, 1H),
6.59 (d, J 1.9 Hz, 1H), 6.48 (d, J 1.9 Hz, 1H), 6.17 (d,
J 7.7 Hz, 1H), 5.90 (dd, J 3.6, 9.9 Hz, 1H), 5.68 (t, J
9.3 Hz, 1H), 5.51 (t, J 10.0 Hz, 1H), 5.49 (m, 1H),
5.30–5.12 (m, 2H), 5.25 (s, 2H), 5.14 (s, 2H), 4.63 (m,
1H), 4.18–3.95 (m, 3H), 4.02 (s, 3H), 3.99 (s, 3H), 3.81