2628
M. Kishida, H. Akita / Tetrahedron: Asymmetry 16 (2005) 2625–2630
(4:1–2:1)] to afford 9 with a by-product, which was
recrystallized from acetone/n-hexane to give pure 9
129.22, 129.16, 129.1, 128.8, 128.7, 128.5 (2C), 128.42
(2C), 128.38 (2C), 128.36 (2C), 128.3 (2C), 128.2 (2C),
117.5, 100.4, 99.7, 73.8, 72.9, 71.9, 70.2 (2C), 69.7,
69.6, 69.1, 68.0, 61.2; Anal. Calcd for C56H48O16: C,
68.83; H, 5.00. Found: C, 68.85; H, 4.95.
(2.07 g, 85%) as a white powder. Mp 197.0–198.2 °C;
27
½aꢀD ¼ ꢁ72.9 (c 0.62, CHCl3); IR (KBr) 1725, 1453,
1260, 1095, 1029, 712 cmꢁ1
;
1H NMR (CDCl3,
400 MHz) d: 8.03–8.00 (m, 4H), 7.94–7.87 (m, 6H),
7.78–7.76 (m, 2H), 7.59–7.54 (m, 1H), 7.53–7.47 (m,
4H), 7.45–7.33 (m, 11H), 7.28–7.24 (m, 2H), 5.82 (t,
1H, J = 9.6 Hz), 5.74 (dd, 1H, J = 6.3, 8.6 Hz), 5.68–
5.65 (m, 1H), 5.61 (dd, 1H, J = 3.0, 8.8 Hz), 5.55 (dddd,
1H, J = 4.8, 6.3, 10.6, 17.2 Hz), 5.42 (dd, 1H, J = 8.1,
9.8 Hz), 5.37 (t, 1H, J = 9.6 Hz), 5.09 (dddd, 1H,
J = 1.2, 1.5, 3.3, 17.2 Hz), 5.03 (dddd, 1H, J = 1.2,
1.5, 3.3, 10.6 Hz), 4.84 (d, 1H, J = 6.3 Hz), 4.72 (d,
1H, J = 7.8 Hz), 4.27 (dd, 1H, J = 4.0, 12.8 Hz), 4.09
(dd, 1H, J = 1.8, 11.1 Hz), 4.04–3.97 (m, 2H), 3.86
(dd, 1H, J = 2.2, 12.9 Hz), 3.84–3.77 (m, 2H); 13C
NMR (CDCl3, 100 MHz) d: 165.7, 165.6, 165.5, 165.3,
165.2, 165.0, 133.5, 133.4 (3C), 133.15, 133.11, 133.0,
129.85 (2C), 129.81 (6C), 129.72 (2C), 129.69 (2C),
129.35, 129.31, 129.2, 129.0, 128.8, 128.7, 128.46
(2C), 128.45 (2C), 128.41 (2C), 128.40 (2C), 128.3
(2C), 128.2 (2C), 117.5, 100.9, 99.5, 73.8, 72.9, 71.8,
70.4, 69.81, 69.75, 69.4, 68.4, 68.3, 62.5; Anal. Calcd
for C56H48O16: C, 68.85; H, 4.95. Found: C, 68.86; H,
5.04.
4.6. Cinnamyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4-tri-O-ben-
zoyl-a-L-arabinopyranosyl)-b-D-glucopyranoside 11
A mixture of 9 (0.489 g, 0.50 mmol), phenylboronic acid
(0.073 g, 0.60 mmol), copper(II) acetate (0.182 g,
1.0 mmol), lithium acetate (0.099 g, 1.5 mmol), and pal-
ladium(II) acetate (0.0112 g, 0.050 mmol) in DMF
(2.0 mL) was stirred for 1 h at 100 °C. This was allowed
to cool to room temperature and the reaction mixture
diluted with EtOAc and water. The organic layer was
washed with 1 M aqueous HCl and brine, dried over
MgSO4, and evaporated to dryness. The residue was
purified by flash column chromatography on silica gel
[25 g, n-hexane/AcOEt (3:1–3:2)] to afford 11 (0.438 g,
82%) as a white solid. The white solid was recrystallized
from ether to give 11 (0.274 g, 52%), a pure white solid
to be analyzed by microanalyses. Mp 182.0–184.0 °C;
27
½aꢀD ¼ þ51.8 (c 0.50, CHCl3); IR (KBr) 1730, 1454,
1
1260, 1093, 710 cmꢁ1; H NMR (CDCl3, 400 MHz) d:
8.04–8.01 (m, 4H), 7.94–7.91 (m, 4H), 7.90–7.87 (m,
2H), 7.79–7.76 (m, 2H), 7.58–7.54 (m, 1H), 7.53–7.46
(m, 4H), 7.43–7.32 (m, 11H), 7.28–7.22 (m, 5H), 7.16–
7.13 (m, 2H), 6.36 (d, 1H, J = 15.9 Hz), 5.87 (ddd, 1H,
J = 4.8, 6.6, 15.9 Hz), 5.82 (t, 1H, J = 9.8 Hz), 5.76
(dd, 1H, J = 6.6, 8.8 Hz), 5.66 (ddd, 1H, J = 2.0, 3.6,
4.0 Hz), 5.61 (dd, 1H, J = 3.6, 8.8 Hz), 5,45 (dd, 1H,
J = 8.1, 9.8 Hz), 5.38 (t, 1H, J = 9.8 Hz), 4.85 (d,
1H, J = 6.3 Hz), 4.76 (d, 1H, J = 8.1 Hz), 4.27 (dd, 1H,
J = 4.0, 13.1 Hz), 4.15–4.00 (m, 2H), 4.05–4.00 (m,
1H), 3.93 (ddd, 1H, J = 1.0, 6.9, 13.8 Hz), 3.87–3.82
(m, 2H); 13C NMR (CDCl3, 100 MHz) d: 165.7, 165.6,
165.5, 165.4, 165.2, 165.0, 136.3, 133.5, 133.4 (3C),
133.15, 133.13, 132.7, 129.9 (4C), 129.8 (8C), 129.7
(2C), 129.4, 129.3, 129.2, 129.0, 128.8, 128.7, 128.49
(2C), 128.45 (4C), 128.4 (2C), 128.3 (2C), 128.2 (2C),
127.7, 126.4 (2C), 124.2, 101.0, 99.4, 73.8, 72.9, 71.9,
70.4, 69.9, 69.8, 69.1, 68.5, 68.4, 62.6; Anal. Calcd for
C62H52O16: C, 70.71; H, 4.98. Found: C, 70.37; H, 5.04.
4.5. Allyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4-tri-O-benzoyl-b-
D-xylopyranosyl)-b-D-glucopyranoside 10
A 50-mL three-necked round-bottom flask covered with
aluminum foil was charged with 6 (1.05 g, 2.0 mmol),
2,3,4-tri-O-benzoyl-a-D-xylopyranosyl
bromide
57
(2.09 g, 4.0 mmol), tetramethylurea (0.69 g, 6.0 mmol),
and CH2Cl2 (8.0 mL). To this solution was added
AgOTf (1.02 g, 4.0 mmol) at 0 °C under an argon atmo-
sphere and stirred for 12 h at room temperature. The
reaction mixture was quenched with saturated aqueous
NaHCO3 and extracted with AcOEt. The organic layer
was washed with brine, dried over MgSO4, and evapo-
rated to dryness. The residue was purified by flash col-
umn chromatography on silica gel [100 g, n-hexane/
AcOEt (4:1–2:1)] to afford 10 with a by-product, which
was recrystallized from acetone/n-hexane to afford
a pure 10 (1.29 g, 67%) as a white powder. Mp 196.8–
27
197.3 °C; ½aꢀD ¼ ꢁ24.9 (c 0.51, CHCl3); IR (KBr)
4.7. 4-Methoxycinnamyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4-
tri-O-benzoyl-a-L-arabinopyranosyl)-b-D-glucopyranoside
12
1729, 1261, 1177, 1101, 1029, 710 cmꢁ1
;
1H NMR
(CDCl3, 400 MHz) d: 8.05–7.96 (m, 6H), 7.94–7.89 (m,
4H), 7.79–7.76 (m, 2H), 7.55–7.47 (m, 5H), 7.42–7.31
(m, 11H), 7.27–7.23 (m, 2H), 5.84 (t, 1H, J = 9.6 Hz),
5.76 (t, 1H, J = 7.3 Hz), 5.61 (dddd, 1H, J = 4.5, 6.1,
10.4, 17.4 Hz), 5.46 (dd, 1H, J = 8.1, 9.6 Hz), 5.42 (t,
1H, J = 9.6 Hz), 5.40 (dd, 1H, J = 5.3, 7.3 Hz), 5.26
(dt, 1H, J = 4.3, 7.3 Hz), 5.14 (tdd, 1H, J = 1.5, 3.3,
17.4 Hz), 5.06 (tdd, 1H, J = 1.5, 3.3, 10.4 Hz), 4.91 (d,
1H, J = 5.3 Hz), 4.75 (d, 1H, J = 8.1 Hz), 4.40 (dd,
1H, J = 4.3, 12.1 Hz), 4.10 (tdd, 1H, J = 1.5, 4.5,
13.4 Hz), 4.08–3.99 (m, 2H), 3.88 (tdd, 1H, J = 1.5,
6.1, 13.4 Hz), 3.81 (dd, 1H, J = 7.0, 11.4 Hz), 3.68 (dd,
1H, J = 7.3, 12.1 Hz); 13C NMR (CDCl3, 100 MHz) d:
165.7, 165.5, 165.4, 165.3, 165.03, 165.00, 133.5,
133.38, 133.35, 133.3, 133.14, 133.11, 133.07, 129.9
(4C), 129.8 (4C), 129.73 (2C), 129.71 (2C), 129.3,
A
mixture of
9
(0.489 g, 0.50 mmol), 4-meth-
oxyphenylboronic acid (0.091 g, 0.60 mmol), copper(II)
acetate (0.182 g, 1.0 mmol), lithium acetate (0.099 g,
1.5 mmol), and palladium(II) acetate (0.0112 g,
0.050 mmol) in DMF (2.0 mL) was stirred for 1 h at
100 °C. This was allowed to cool to room temperature
and the reaction mixture diluted with EtOAc and water.
The organic layer was washed with 1 M aqueous HCl
and brine, dried over MgSO4, and evaporated to dry-
ness. The residue was purified by flash column chroma-
tography on silica gel [25 g, n-hexane/AcOEt (3:1–3:2)]
to afford 12 (0.506 g, 93%) as a white solid. The white
solid was recrystallized from acetone to provide 12
(0.137 g, 25%), a pure white solid to be analyzed by