ORDER
REPRINTS
Synthesis of 3-O-b-D- and 40-O-b-D-Glucopyranosides
1571
(c 0.25, MeOH); (Found: C, 59.63; H, 4.99. C32H34O14 requires C, 59.81; H,
5.33%); nmax (KBr disc)/cm21 1756 (CO); dH (400 MHz, DMSO-d6) 7.51
(2H, d, J 8.4, H-20, H-60), 7.11 (2H, d, J 8.4, H-30, H-50), 7.05–6.94 (4H, m,
H-2, H-4, 2 ꢁ vinylic CH), 6.7 (1H, s, H-6), 5.34–5.27 (2H, m, H-200,
H-300), 5.2–5.13 (2H, m, anomeric H-100, H-400), 4.32–4.27 (1H, m, H-600A),
4.21–4.18 (1H, m, H-600B), 3.94–3.92 (1H, m, H-500), 2.32 (6H, s,
2 ꢁ CH3), 2.09 (3H, s, CH3), 2.07 (6H, s, 2 ꢁ CH3), and 2.05 (3H, s, CH3);
dC (100 MHz, DMSO-d6) 171.1 (CO), 170.8 (CO), 170.0 (CO), 169.9 (CO),
169.8 (CO), 158.1 (C-3), 150.9 (C-40), 150.2 (C-6), 150.0 (C-1), 140.2
(C-2), 135.0 (C-10), 130.1 (vinylic C), 128.2 (vinylic C), 127.9 (C-60), 122.5
(C-50), 99.3 (anomeric C-100), 73.2 (C-300), 72.6 (C-200), 71.6 (C-400), 68.9
(C-500), 62.6 (C-600), 21.7 (CH3), 21.2 (CH3), and 21.1 (CH3).
trans-Resveratrol-3-O-b-D-glucopyranoside 2. To a suspension of 9
(0.55 g, 0.86 mmol) in methanol (30 cm3) at room temperature was added a
0.2 M methanolic solution of sodium methoxide (30 cm3). The resulting mix-
ture was stirred for 1 hr, whereupon sufficient Dowex 50WX8-100 ion
exchange resin was added in portions to maintain pH ꢀ2. The resin was
filtered off and washed with methanol (5 cm3). The combined filtrate was
evaporated (408C, water-aspirator pressure), and the residue was dried at 458C
over phosphorus pentoxide to give the product as a beige solid (0.31 g, 94%)
of m.p. 226–2298C (lit.,[28] 228–2308C); [a]2D5 ¼ 2648 (c 0.32, MeOH)
(lit.,[25] [a]2D5 ¼ 2628); (Found: C, 58.16; H, 6.32. C20H22O81 3H2O requires
.
C, 57.97; H, 6.00%); nmax (KBr disc)/cm21 3367 (OH, very broad) and 1592;
dH (400 MHz, DMSO-d6) 9.59 (1H, s, phenolic OH), 9.46 (1H, s, phenolic
OH), 7.40 (2H, d, J 8.2, H-20, H-60), 7.03 (1H, d, J 16.3, vinylic CH), 6.86
(1H, d, J 16.3, vinylic CH), 6.76 (2H, d, J 8.2, H-30, H-50), 6.7 (1H, s, H-6),
6.6 (1H, s, H-2), 6.3 (1H, s, H-4), 4.80 (1H, d, J 7.3, anomeric H-100), 3.73–
3.71 (1H, m, H-600A), and 3.69–3.14 (5H, m, H-200, H-300, H-400, H-500,
H-600B); dC (100 MHz, DMSO-d6) 159.9 (C-5), 159.3 (C-3), 158.3 (C-40),
140.3 (C-1), 129.5 (vinylic C), 128.9 (C-60), 126.2 (vinylic C), 116.5 (C-50),
108.2 (C-2), 105.7 (C-6), 103.7 (C-4), 101.6 (anomeric C-100), 78.13 (C-500),
77.69 (C-300), 74.29 (C-200), 70.6 (C-400), and 61.7 (C-600).
4-Iodophenyl-2,3,4,6-tetra-O-acetyl-b-D-glucopyranoside 12. To a stir-
red solution of 4-iodophenol (1.0 g, 4.54 mmol) and acetobromo-a-D-glucose
5 (2.80 g, 6.82 mmol) in acetonitrile at room temperature was added silver
carbonate (1.88 g, 6.82 mmol) in portions. The resulting mixture was stirred
in the dark for 48 hr, and then filtered through a short Celite pad. The filtrate
was evaporated to dryness (408C, water-aspirator pressure) to leave an oil that
solidified on standing. Recrystallization from a dichloromethane/isopropanol
mixture afforded the product as a white solid (0.75g, 30%) of m.p. 142–1438C;
[a]2D5 ¼ 251.68 (c 0.29, MeOH); (Found: C, 43.84; H, 4.33. C20H23IO10
requires C, 43.65; H, 4.21%); nmax (KBr disc)/cm21 1747 (CO); dH