832
J. Sun et al. / Carbohydrate Research 338 (2003) 827–833
4 H, Phth), 5.92–5.79 (m, 2 H), 5.36 (d, 1 H, J 8.2),
5.32–5.00 (m, 9 H), 4.71 (d, 1 H, J 6.9), 4.64 (d, 1 H,
J 4.5), 4.50 (m, 2 H), 4.27 (dd, 1 H, J 8.5, 10.7),
4.10–3.98 (m, 2 H), 3.89–3.62 (m, 5 H), 3.57 (dd, 1 H,
J 3.2, 12.0), 3.10 (dd, 1 H, J 4.6, 12.0), 2.84 (m, 1 H),
1.08, 0.91, 0.89, 0.84, 0.66, 0.55, 0.43 (s each, 3 H each,
7×Me); ESIMS (m/z): 1370.4 [M+Na+].
103.7, 90.8, 80.7, 76.8, 76.0, 74.5, 73.1, 72.3, 69.9, 69.7,
69.1, 67.5 67.3, 66.0, 58.1, 57.1, 47.4, 43.2, 43.1, 40.9,
40.2, 38.2, 35.1, 34.3, 34.1,33.8, 31.9, 29.0, 28.8, 27.3,
26.7, 24.8, 24.2, 23.4, 23.3, 19.6, 18.1, 17.4, 16.2, 11.2.
ESIMS (m/z): 989.7 [M+Na+].
3.16. 28-Allyl-O-oleanate-3-yl 2,3,4-tri-O-acetyl-a-
arabinopyranosyl-(12)-3,4-di-O-acetyl-a- -arabino-
pyranosyl-(16)-3,4-di-O-acetyl-2-deoxy-2-acetamido-
b- -glucopyranoside (23)
L-
L
3.14. 28-O-Allyl-oleanate-3-yl 2,3,4-tri-O-benzoyl-a-
arabinopyranosyl-(12)-3,4-di-O-acetyl-a- -arabino-
pyranosyl-(16)-3,4-di-O-acetyl-2-deoxy-2-phthal-
imido-b- -glucopyranoside (21)
L-
D
L
A solution of 21 (75 mg, 0.055 mmol) in BuOH (2 mL)
and NH2CH2CH2NH2 (2 mL) was stirred at 90 °C
overnight, and then concentrated to give a residue. The
residue was coevaporated with toluene and EtOH twice
and then dissolved in 1:1 pyridine–Ac2O (2 mL). The
resulting mixture was stirred at rt for 4 h and then
concentrated to give a residue, which was subjected to
silica gel column chromatography (4:4:0.1 petroleum
ether–EtOAc–EtOH) to provide 23 (48 mg, 80%) as a
white amorphous solid: Rf 0.39 (40:1 CH2Cl2–
D
A similar procedure for the synthesis of 20 was em-
ployed for the synthesis of 21. Compound 21 (319 mg,
76%) was obtained after silica gel column chromatogra-
phy (1:1 petroleum ether–EtOAc) as a white amor-
phous solid: Rf 0.37 (3:2 petroleum ether–EtOAc); [h]D20
+103.3° (c 0.60, CHCl3); 1H NMR (300 MHz, CDCl3):
l 8.06–7.31 (m, 19 H, Bz+Phth), 5.85 (m+t, 2 H, J
9.6), 5.72 (br s, 1 H), 5.67 (dd, 1 H, J 6.3, 8.6), 5.57 (dd,
1 H, J 3.4, 8.6), 5.39 (d, 1 H, J 8.2), 5.32–5.05 (m, 5 H),
4.92 (dd, 1 H, J 3.3, 9.0), 4.67 (d, 1 H, J 5.5), 4.44 (m,
2 H), 4.31 (dd, 1 H, J 8.3, 10.5), 4.04–3.88 (m, 6 H),
3.59 (dd, 1 H, J 2.2, 9.4), 3.14 (dd, 1 H, J 4.0, 11.5),
2.87 (m, 1 H), 2.04, 1.87 (s each, 3 H each, 2×Ac),
1.89 (s, 6 H, 2×Ac), 1.13, 0.94, 0.92, 0.81, 0.64, 0.54,
0.39 (s each, 3 H each, 7×Me); ESIMS (m/z): 1554.3
[M+Na+]. Anal. Calcd for C86H101NO24·H2O: C,
66.60; H, 6.70; N, 0.90. Found: C, 66.45; H, 6.85; N,
1.15.
1
CH3OH); [h]2D0 +17.9° (c 1.10, CHCl3); H NMR (300
MHz, CDCl3): l 5.88 (m, 1 H, allyl), 5.57 (d, 1 H, J
8.8), 5.30–5.13 (m, 6 H), 5.00 (m, 3 H), 4.68–4.50 (m,
4 H), 4.02–3.65 (m, 8 H), 3.52 (dd, 1 H, J 3.3, 11.8),
3.12 (dd, 1 H, J 4.5, 11.4), 2.88 (m, 1 H), 2.13 (m,
8×Ac), 1.16, 0.92, 0.90, 0.98, 0.76, 0.74, 0.71 (s each, 3
H each, 7×Me); ESIMS (m/z): 1281.5 [M+Na+].
Anal. Calcd for C65H95NO23·H2O: C, 61.16; H, 7.66; N,
1.10. Found: C, 61.02; H, 7.86; N, 1.29.
3.17. Oleanolic acid-3-yl 2,3,4-tri-O-acetyl-a-
arabinopyranosyl-(12)-3,4-di-O-acetyl-a- -arabino-
pyranosyl-(16)-3,4-di-O-acetyl-2-deoxy-2-acetamido-
b- -glucopyranoside (24)
L-
L
3.15. 28-O-Propyl-oleanate-3-yl a-
(12)-a- -arabinopyranosyl-(16)-2-deoxy-2-
acetamido-b- -glucopyranoside (22)
L-arabinopyranosyl-
L
D
D
A mixture of 23 (38 mg, 0.03 mmol) and PdCl2 (2 mg,
0.01 mmol) in abs MeOH (4 mL) was stirred at rt for
48 h, and filtered through a pad of Celite. The filtrates
were concentrated. The residue was subjected to silica
gel column chromatography (2:2:0.1 petroleum ether–
EtOAc–EtOH) to give 24 (16 mg, 44%) as a white
amorphous solid: Rf 0.39 (2:2:0.1 petroleum ether–
EtOAc–EtOH); [h]2D0 +22.0° (c 0.50, CHCl3); 1H
NMR (300 MHz, CDCl3): l 5.56 (m, 1 H), 5.27–4.98
(m, 7 H), 4.67–4.57 (m, 3 H), 4.01 (m, 2 H), 3.85–3.47
(m, 6 H), 1.11, 1.10, 0.91, 0.89, 0.74, 0.73, 0.70 (s each,
3 H each, 7×Me); ESIMS (m/z): 1241.7 [M+Na+].
Anal. Calcd for C62H91NO23·3.5 H2O: C, 58.11; H,
7.71; N, 1.09. Found: C, 57.92; H, 7.45; N, 1.10.
A
solution of 21 (102 mg, 0.075 mmol) and
NH2NH2·H2O (2 mL) in EtOH (95%, 4 mL), after
stirring at 80 °C for 6 h, was concentrated and coevap-
orated with toluene twice to give a residue. The residue
was dissolved in 1:1 pyridine–Ac2O (4 mL). The result-
ing solution, after stirring for 4 h, was concentrated.
The residue was then dissolved in abs MeOH (4 mL)
containing MeONa (70 mg). The solution was stirred at
rt overnight, and then neutralized with Dowex-50 (H+).
Filtration and evaporation of the solvent gave a crude
product, which was purified by silica gel column chro-
matography (3:1 CHCl3–MeOH) to give 22 (18 mg,
24%) as a white amorphous solid: Rf 0.45 (30:5:4
EtOAc–CH3OH–H2O); 1H NMR (300 MHz,
CD3OD): l 5.26 (s, 1 H, H-12), 4.54 (d, 1 H, J 5.8),
4.51 (d, 1 H, J 6.8), 4.45 (d, 1 H, J 8.2), 4.08–4.43 (m,
17 H), 3.32 (m, 2 H), 3.19 (dd, 1 H, J 4.1, 11.2), 2.90
(m, 1 H), 1.96 (s, 3 H, NAc), 1.17, 0.97, 0.95, 0.94, 0.92,
0.77, 0.76 (s each, 3 H, 7×Me); 13C NMR (75 MHz,
CD3OD): l 179.9, 173.7, 145.3, 124.2, 106.1, 105.2,
3.18. Preparation of oleanolic acid-3-yl a-
ranosyl-(12)-a- -arabinopyranosyl-(16)-2-
acetamido-2-deoxy-b- -glucopyranoside (1)
L-arabinopy-
L
D
A solution of 24 (29 mg, 0.024 mmol) in abs MeOH (4
mL) containing MeONa (50 mg) was stirred at rt