10564
M. Kishida, H. Akita / Tetrahedron 61 (2005) 10559–10568
80 8C. Allowed to cool to room temperature, the reaction
mixture was diluted with EtOAc and washed with 1 M HCl
and brine. The organic layer was evaporated to dryness and
the residue was purified by flash chromatography to afford
4d (0.27 g, 52%) as a white solid. The white solid was
recrystallized from AcOEt/n-hexane to give 4d (0.22 g,
42%), a pure white powder. Mp: 185.0–187.0 8C; [a]D29
K32.6 (c 0.24, CDCl3); IR (KBr) 3399, 1753, 1517, 1370,
1228, 1129, 1040, 978 cmK1; 1H NMR (CDCl3, 400 MHz)
d: 6.91–6.85 (m, 3H), 6.51 (d, JZ15.6 Hz, 1H), 6.06 (ddd,
JZ5.5, 6.5, 15.6 Hz, 1H), 5.63 (s, 1H), 5.22 (t, JZ9.6 Hz,
1H), 5.11 (t, JZ9.6 Hz, 1H), 5.04 (dd, JZ8.0, 9.6 Hz, 1H),
4.62 (d, JZ8.0 Hz, 1H), 4.47 (ddd, JZ1.5, 5.6, 12.6 Hz,
1H), 4.30–4.23 (m, 2H), 4.17 (dd, JZ2.0, 12.1 Hz, 1H),
3.92 (s, 3H), 3.70 (ddd, JZ2.0, 4.5, 9.6 Hz, 1H), 2.08 (s,
3H), 2.05 (s, 3H), 2.02 (s, 3H), 2.01 (s, 3H); 13C NMR
(CDCl3, 100 MHz) d: 170.7, 170.3, 169.40, 169.35, 146.6,
145.8, 133.3, 128.9, 122.1, 120.4, 114.4, 108.3, 99.5, 72.9,
71.8, 71.4, 70.1, 68.4, 62.0, 55.9, 20.72, 20.60, 20.59;
HR-MS (FAB-MS) m/z: 511.1840 (MC1)C; Calcd for
C24H30O12 m/z: 511.1815 (MC1)C.
5.3.7. 2-Methoxycinnamyl 2,3,4,6-tetra-O-acetyl-b-D-
glucopyranoside (4g). Obtained in 74% yield as a white
solid. The white solid was recrystallized from AcOEt/
n-hexane to give 4g in 42% yield, pure colorless needles to
be analyzed by microanalyses. Mp: 88.9–89.5 8C; [a]D27
K25.1 (c 0.33, MeOH); IR (KBr) 1745, 1372, 1224, 1046,
984 cmK1; 1H NMR (CDCl3, 400 MHz) d: 7.42 (dd, JZ1.5,
7.6 Hz, 1H), 7.25–7.22 (m, 1H), 6.95–6.86 (m, 3H), 6.21
(ddd, JZ5.7, 7.0, 16.1 Hz, 1H), 5.21 (t, JZ9.6 Hz, 1H),
5.11 (t, JZ9.6 Hz, 1H), 5.05 (dd, JZ8.1, 9.6 Hz, 1H), 4.63
(d, JZ8.1 Hz, 1H), 4.49 (ddd, JZ1.5, 5.6, 13.1 Hz, 1H),
4.30 (ddd, JZ1.0, 6.5, 13.1 Hz, 1H), 4.27 (dd, JZ5.0,
12.6 Hz, 1H), 4.16 (dd, JZ2.5, 12.1 Hz, 1H), 3.85 (s, 3H),
3.70 (dd, JZ2.5, 5.0, 9.6 Hz, 1H), 2.09 (s, 3H), 2.06 (s, 3H),
2.02 (s, 3H), 2.00 (s, 3H); 13C NMR (CDCl3, 100 MHz) d:
170.7, 170.3, 169.39, 169.38, 156.7, 129.0, 128.4, 127.0,
125.4, 124.9, 120.7, 110.8, 99.2, 72.9, 71.8, 71.3, 70.2, 68.4,
62.0, 55.4, 20.69, 20.65, 20.60, 20.57. Anal. Found: C,
58.25; H, 6.08%. Calcd for C24H30O11: C, 58.29; H, 6.12%.
5.3.8. 3,4-Dimethoxycinnamyl 2,3,4,6-tetra-O-acetyl-b-
D-glucopyranoside (4h). Obtained in 42% yield as a white
solid. The white solid was recrystallized from AcOEt/
n-hexane to give 4h in 32% yield, pure colorless needles to
be analyzed by microanalyses. Mp: 78.0–79.5 8C; [a]D27
K30.3 (c 0.29, MeOH); IR (KBr) 1747, 1516, 1444, 1369,
5.3.5. 3,4,5-Trimethoxycinnamyl 2,3,4,6-tetra-O-acetyl-
b-D-glucopyranoside (4e). Obtained in 67% yield as a
white solid. The white solid was recrystallized from AcOEt/
n-hexane to give 4e in 46% yield, pure colorless needles to
be analyzed by microanalyses. Mp: 131.0–132.0 8C; [a]D29
K30.3 (c 0.29, MeOH); IR (KBr) 1752, 1583, 1506, 1422,
1371, 1335, 1228, 1128, 1043, 976 cmK1; 1H NMR (CDCl3,
400 MHz) d: 6.61 (s, 2H), 6.52 (d, JZ16.1 Hz, 1H), 6.14
(ddd, JZ5.5, 6.5, 16.1 Hz, 1H), 5.22 (t, JZ9.6 Hz, 1H),
5.12 (t, JZ9.6 Hz, 1H), 5.05 (dd, JZ8.1, 9.6 Hz, 1H), 4.63
(d, JZ8.1 Hz, 1H), 4.49 (ddd, JZ1.5, 5.5, 12.6 Hz, 1H),
4.30–4.23 (m, 2H), 4.17 (dd, JZ2.5, 12.6 Hz, 1H), 3.88 (s,
6H), 3.85 (s, 3H), 3.71 (ddd, JZ2.5, 4.5, 9.6 Hz, 1H), 2.08
(s, 3H), 2.06 (s, 3H), 2.03 (s, 3H), 2.01 (s, 3H); 13C NMR
(CDCl3, 100 MHz) d: 170.6, 170.3, 169.4, 169.3, 153.3,
138.1, 133.0, 132.1, 124.0, 103.7, 99.6, 72.9, 71.8, 71.3,
69.8, 68.4, 61.9, 60.9, 56.2, 20.70, 20.59, 20.57. Anal.
Found: C, 56.01; H, 6.10%. Calcd for C26H35O13: C, 56.31;
H, 6.18%.
1225, 1166, 1038, 981, 609 cmK1 1H NMR (CDCl3,
;
400 MHz) d: 6.95–6.90 (m, 2H), 6.82 (d, JZ8.0 Hz, 1H),
6.53 (d, JZ16.1 Hz, 1H), 6.09 (td, JZ6.4, 16.1 Hz, 1H),
5.22 (t, JZ9.6 Hz, 1H), 5.09 (t, JZ9.6 Hz, 1H), 5.05 (dd,
JZ8.1, 9.6 Hz, 1H), 4.63 (d, JZ8.1 Hz, 1H), 4.47 (dd, JZ
5.5, 12.6 Hz, 1H), 4.29–4.23 (m, 2H), 4.17 (dd, JZ2.0,
12.6 Hz, 1H), 3.90 (s, 3H), 3.89 (s, 3H), 3.71 (ddd, JZ2.5,
4.5, 9.6 Hz, 1H), 2.09 (s, 3H), 2.06 (s, 3H), 2.03 (s, 3H), 2.01
(s, 3H); 13C NMR (CDCl3, 100 MHz) d: 170.6, 170.3,
169.4, 169.3, 149.12, 149.05, 133.1, 129.4, 122.4, 119.8,
111.1, 108.9, 99.5, 72.9, 71.8, 71.4, 70.0, 61.9, 55.9, 55.8,
20.71, 20.59, 20.57. Anal. Found: C, 57.05; H, 6.09%. Calcd
for C25H32O12: C, 57.25; H, 6.15%.
5.3.9. 4-Chlorocinnamyl 2,3,4,6-tetra-O-acetyl-b-D-
glucopyranoside (4i). Obtained in 74% yield as a white
solid. The white solid was recrystallized from ether/
n-hexane to give 4i in 51% yield, a pure white powder to
be analyzed by microanalyses. Mp: 92.3–94.0 8C; [a]D29
K31.4 (c 0.44, CHCl3); IR (KBr) 1748, 1369, 1229, 1169,
1041, 987, 913 cmK1; 1H NMR (CDCl3, 400 MHz) d: 7.29
(s, 4H), 6.54 (d, JZ16.1 Hz, 1H), 6.19 (ddd, JZ5.5, 6.5,
16.1 Hz, 1H), 5.22 (t, JZ9.6 Hz, 1H), 5.11 (t, JZ9.6 Hz,
1H), 5.05 (dd, JZ8.1, 9.6 Hz, 1H), 4.61 (d, JZ8.1 Hz, 1H),
4.49 (ddd, JZ1.5, 5.5, 13.1 Hz, 1H), 4.29–4.23 (m, 2H),
4.16 (dd, JZ2.0, 12.6 Hz, 1H), 3.71 (ddd, JZ2.0, 4.6,
9.6 Hz, 1H), 2.08 (s, 3H), 2.05 (s, 3H), 2.03 (s, 3H), 2.01 (s,
3H); 13C NMR (CDCl3, 100 MHz) d: 170.6, 170.3, 169.4,
169.3, 134.9, 133.1, 131.6, 128.8, 127.7, 125.2, 99.7, 72.8,
71.8, 71.3, 69.7, 68.4, 61.9, 20.70, 20.59, 20.57. Anal.
Found: C, 55.08; H, 5.43%. Calcd for C23H27ClO10: C,
55.37; H, 5.25%, Cl, 7.11%.
5.3.6. 3-Methoxycinnamyl 2,3,4,6-tetra-O-acetyl-b-D-
glucopyranoside (4f). Obtained in 86% yield as a white
solid. The white solid was recrystallized from AcOEt/
n-hexane to give 4f in 54% yield, a pure white powder to be
analyzed by microanalyses. Mp: 102.0–103.5 8C; [a]D27
K31.1 (c 0.50, MeOH); IR (KBr) 1743, 1600, 1439,
1
1369, 1325, 1227, 1169, 1040, 986, 913 cmK1; H NMR
(CDCl3, 400 MHz) d: 7.22 (dd, JZ7.6, 8.1 Hz, 1H), 6.96 (d,
JZ7.6 Hz, 1H), 6.92 (d, JZ2.5 Hz, 1H), 6.81 (dd, JZ2.5,
8.1 Hz, 1H), 6.56 (d, JZ15.6 Hz, 1H), 6.21 (td, JZ6.5,
15.6 Hz, 1H), 5.21 (t, JZ9.6 Hz, 1H), 5.11 (t, JZ9.6 Hz,
1H), 5.05 (dd, JZ7.6, 9.6 Hz, 1H), 4.62 (d, JZ7.6 Hz, 1H),
4.49 (ddd, JZ1.5, 5.6, 13.1 Hz, 1H), 4.31–4.24 (m, 2H),
4.16 (dd, JZ2.5, 12.1 Hz, 1H), 3.82 (s, 3H), 3.71 (ddd, JZ
2.5, 5.0, 9.6 Hz, 1H), 2.09 (s, 3H), 2.06 (s, 3H), 2.02 (s, 3H),
2.01 (s, 3H); 13C NMR (CDCl3, 100 MHz) d: 170.7, 170.2,
169.4, 169.3, 159.8, 137.8, 132.9, 129.6, 124.8, 119.1,
113.5, 111.9, 99.6, 72.9, 71.8, 71.3, 69.8, 68.4, 61.9, 55.2,
20.69, 20.58, 20.56. Anal. Found: C, 58.23; H, 6.09%. Calcd
for C24H30O11: C, 58.29; H, 6.12%.
5.3.10. 4-Cyanocinnamyl 2,3,4,6-tetra-O-acetyl-b-D-
glucopyranoside (4j). Obtained in 75% yield as a white
solid. The white solid was recrystallized from ether/
n-hexane to get 4j in 51% yield, a pure white solid. Mp: