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Arch. Pharm. Chem. Life Sci. 2011, 344, 505–513
H-12), 5.50 (d, 1H, NH, J ¼ 8.6 Hz), 4.56 (m, 2H, H-3 and Asp-CH),
3.69 (s, 3H, OMe), 3.68 (s, 3H, Asp-OMe), 3.03 (dd, 1H, Asp-CHH’,
J ¼ 17.1, 3.9 Hz), 2.83 (m, 1H, Asp-CHH’), 2.80 (m, 1H, H-1), 2.35
(s, 1H, H-9), 2.08 (dd, 1H, H-18, J ¼ 13.4, 3.3 Hz), 2.03 (m, 1H, H-
15), 1.99 (m, 1H, H-21), 1.92 (ddd, 1H, H-19, J ¼ 13.8, 4.0, 2.6 Hz),
1.82 (ddd, 1H, H-16, J ¼ 13.6, 13.6, 4.1 Hz), 1.73 (m, 1H, H-2), 1.67
(m, 1H, H-2’), 1.63 (m, 1H, H-7), 1.60 (dd, 1H, H-19’, J ¼ 13.5,
13.5 Hz), 1.58 (m, 1H, H-6), 1.45 (s, 9H, Boc-CH3), 1.43 (m, 1H,
H-6’), 1.41 (m, 1H, H-7’), 1.38 (m, 1H, H-22), 1.36 (s, 3H, H-27), 1.31
(m, 1H, H-22’), 1.31 (m, 1H, H-21’), 1.18 (m, 1H, H-16’), 1.16 (s, 3H,
H-25), 1.15 (s, 3H, H-29), 1.12 (s, 3H, H-26), 1.06 (m, 1H, H-1’), 1.02
(m, 1H, H-15’), 0.87 (s, 3H, H-24), 0.85 (s, 3H, H-23), 0.80 (m, 1H,
H-5), 0.79 (s, 3H, H-28) ppm; 13C-NMR (125 MHz, CDCl3): d ¼ 199.9
(C-11), 176.9 (C-30), 171.5 (Asp-COOMe), 170.7 (Asp-COO), 169.2
(C-13), 155.4 (Boc-COO), 128.5 (C-12), 82.4 (C-3), 79.9 (Boc-quart.-C),
61.6 (C-9), 55.0 (C-5), 51.9 (Asp-OMe), 51.7 (OMe), 50.2 (Asp-CHNH2),
48.4 (C-18), 45.4 (C-8), 44.0 (C-20), 43.2 (C-14), 41.1 (C-19), 38.7 (C-1),
38.1 (C-4), 37.7 (C-22), 36.9 (C-10), 36.6 (Asp-CH2), 32.7 (C-7), 31.8
(C-17), 31.1 (C-21), 28.5 (C-28), 28.3 (C-29), 27.8 (C-23), 26.5 (C-16),
26.4 (C-15), 23.4 (C-2), 23.3 (C-27), 18.7 (C-26), 17.3 (C-6), 16.7 (C-24),
16.3 (C-25) ppm; MS (ESI, MeOH): m/z (%) ¼ 714.2 ([M þ H]þ, 5),
736.4 ([M þ Na]þ, 100), 1093.3 ([3 M þ 2 Na]2þ, 12), 1450.0
([2 M þ Na]þ, 22); anal. calcd. for C41H63NO9 (713.94): C, 68.97;
H, 8.89; N, 1.96; found: C, 68.76; H, 9.04; N, 1.79.
Methyl 3b 3-(O-methyl-L-asparagyl)-11-oxo-olean-12-en-
30-oate (12)
Obtained from 10 (550 mg, 0.79 mmol) by method B as a color-
less powder; yield: 360 mg, 83%; mp 226–2298C (dec.); RF ¼ 0.73
(dichloromethane/methanol 9:1); [a]D ¼ 111.728 (c ¼ 0.47,
CHCl3); UV-VIS (methanol): lmax (log e) ¼ 249 nm (3.62); IR
(KBr): n ¼ 3365 (br), 2962 (m), 2874 (m), 1739 (s), 1727 (s), 1652
(s), 1614 (w), 1438 (m), 1389 (m), 1318 (w), 1264 (m), 1218 (m),
1186 (m), 1161 (m), 1086 (w), 1026 (m), 988 (w), 959 (w), 904 (w),
879 (w), 851 (w), 826 (w), 771 (w), 670 (w), 590 (w), 543 (w) cmꢂ1
;
1H-NMR (400 MHz, CDCl3): d ¼ 5.67 (s, 1H, H-12), 4.58 (dd, 1H,
H-3, J ¼ 11.6, 4.9 Hz), 3.80 (dd, 2H, Asp-CH, J ¼ 7.1, 4.7 Hz), 3.70
(s, 3H, OMe), 3.69 (s, 3H, Asp-OMe), 2.83 (m, 1H, Asp-CHH’), 2.81
(m, 1H, H-1), 2.72 (dd, 1H, Asp-CHH’, J ¼ 16.5, 7.2 Hz), 2.36 (s, 1H,
H-9), 2.08 (dd, 1H, H-18, J ¼ 12.8, 3.6), 2.03 (m, 1H, H-15), 1.99
(m, 1H, H-21), 1.92 (ddd, 1H, H-19, J ¼ 13.5, 3.9, 2.7 Hz), 1.82 (ddd,
1H, H-16, J ¼ 13.6, 13.6, 4.2 Hz), 1.73 (m, 1H, H-2), 1.69 (m, 1H, H-
7), 1.63 (m, 1H, H-2’), 1.61 (dd, 1H, H-19’, J ¼ 13.5, 13.5 Hz), 1.57
(m, 1H, H-6), 1.48 (m, 1H, H-6’), 1.43 (m, 1H, H-7’), 1.40 (m, 1H,
H-22), 1.36 (s, 3H, H-27), 1.31 (m, 1H, H-22’), 1.31 (m, 1H, H-21’),
1.18 (m, 1H, H-16’), 1.16 (s, 3H, H-25), 1.15 (s, 3H, H-29), 1.13 (s, 3H,
H-26), 1.06 (m, 1H, H-1’), 1.01 (m, 1H, H-15’), 0.87 (s, 3H, H-24), 0.87
(s, 3H, H-23), 0.81 (m, 1H, H-5), 0.80 (s, 3H, H-28) ppm; 13C-NMR
(125 MHz, CDCl3): d ¼ 199.9 (C-11), 176.9 (C-30), 173.9 (Asp-COO),
171.6 (Asp-COOMe), 169.2 (C-13), 128.5 (C-12), 81.8 (C-3), 61.6 (C-9),
55.0 (C-5), 51.8 (Asp-OMe), 51.7 (OMe), 51.5 (Asp-CH), 48.4 (C-18),
45.4 (C-8), 44.0 (C-20), 43.2 (C-14), 41.1 (C-19), 38.7 (C-1), 38.6 (Asp-
CH2), 38.1 (C-4), 37.7 (C-22), 36.9 (C-10), 32.7 (C-7), 31.8 (C-17), 31.1
(C-21), 28.5 (C-28), 28.3 (C-29), 28.0 (C-23), 26.5 (C-16), 26.4 (C-15),
23.5 (C-2), 23.3 (C-27), 18.7 (C-26), 17.3 (C-6), 16.7 (C-24), 16.3 (C-25)
ppm; MS (ESI, MeOH): m/z (%) ¼ 614.2 ([M þ H]þ, 100), 636.3
([M þ Na]þ, 4); anal. calcd. for C36H55NO7 (613.82): C, 70.44;
H, 9.03; N, 2.28; found: C, 70.25; H, 9.19; N, 2.14.
Methyl 3b 3-(Boc-O-methyl-L-glutamyl)-11-oxo-olean-12-
en-30-oate (11)
Obtained from 7 (500 mg, 0.70 mmol) by method E as a colorless
powder; yield: 390 mg, 77%; mp 202–2058C; RF ¼ 0.38 (hexane/
ethyl acetate 7:3); [a]D ¼ 95.048 (c ¼ 0.66, CHCl3); UV-VIS (meth-
anol): lmax (log e) ¼ 250 nm (4.10); IR (KBr): n ¼ 3381 (br), 2951
(s), 2874 (m), 1748 (s), 1726 (s), 1711 (s), 1652 (s), 1509 (m), 1453
(m), 1390 (m), 1366 (m), 1354 (m), 1326 (m), 1264 (m), 1216 (s),
1163 (s), 1087 (w), 1076 (w), 1050 (w), 1026 (m), 984 (m), 918 (w),
882 (w), 825 (w), 772 (w), 538 (w) cmꢂ1; 1H-NMR (400 MHz, CDCl3):
d ¼ 5.67 (s, 1H, H-12), 5.09 (d, 1H, Glu-NH, J ¼ 7.9 Hz), 4.56 (dd,
1H, H-3, J ¼ 11.6, 4.8 Hz), 4.32 (m, 1H, Glu-CHN), 3.69 (s, 3H, Glu-
OMe), 3.68 (s, 3H, OMe), 2.82 (ddd, 1H, H-1, J ¼ 13.7, 3.4, 3.4 Hz),
2.45 (m, 1H, Glu-CHH’COOMe), 2.39 (m, 1H, Glu-CHH’COOMe),
2.36 (s, 1H, H-9), 2.23 (m, 1H, Glu-CHH’CHN), 2.08 (dd, 1H, H-18,
J ¼ 13.7, 3.5 Hz), 2.03 (m, 1 H, H-15), 1.99 (m, 1H, H-21), 1.96
(m, 1H, Glu-CHH’CHN), 1.92 (ddd, 1H, H-19, J ¼ 13.3, 3.3, 2.3 Hz),
1.83 (ddd, 1H, H-16, J ¼ 13.7, 13.7, 4.2 Hz), 1.74 (m, 1H, H-2), 1.66
(m, 1H, H-7), 1.63 (m, 1H, H-2’), 1.61 (dd, 1H, H-19’, J ¼ 13.5,
13.5 Hz), 1.57 (m, 1H, H-6), 1.46 (m, 1H, H-6’), 1.44 (s, 9H, Boc-
CH3), 1.42 (m, 1H, H-7’), 1.39 (m, 1H, H-22), 1.36 (s, 3H, H-27), 1.31
(m, 2H, H-22’ and H-21’), 1.18 (m, 1H, H-16’), 1.17 (s, 3H, H-25), 1.15
(s, 3H, H-29), 1.13 (s, 3H, H-26), 1.07 (m, 1H, H-1’), 1.02 (m, 1H,
H-15’), 0.90 (s, 3H, H-24), 0.88 (s, 3H, H-23), 0.81 (s, 3H, H-28), 0.80
(m, 1H, H-5) ppm; 13C-NMR (125 MHz, CDCl3): d ¼ 199.9 (C-11),
173.2 (Glu-COOMe), 176.9 (C-30), 171.6 (Glu-COO), 169.2 (C-13),
155.3 (Boc-COO), 128.5 (C-12), 82.2 (C-3), 79.9 (Boc-quart.-C), 61.7 (C-
9), 55.0 (C-5), 53.3 (Glu-CHNH), 51.8 (OMe), 48.4 (C-18), 45.4 (C-8),
44.0 (C-20), 43.2 (C-14), 41.1 (C-19), 38.7 (C-1), 38.1 (C-4), 37.7 (C-22),
36.9 (C-10), 32.7 (C-7), 31.8 (C-17), 31.1 (C-21), 30.2 (Glu-
CH2COOMe), 28.5 (C-28), 28.3 (C-29), 28.3 (Boc-CH3), 28.1 (C-23),
28.0 (Glu-CH2CHNH), 26.5 (C-16), 26.4 (C-15), 23.6 (C-2), 23.3 (C-27),
18.7 (C-26), 17.3 (C-6), 16.8 (C-24), 16.4 (C-25) ppm; MS (ESI, MeOH):
m/z (%) ¼ 750.4 ([M þ Na]þ, 100), 1114.3 ([3 M þ 2 Na]2þ, 22),
1478.1 ([2 M þ Na]þ, 24); anal. calcd. for C42H65NO9 (727.97):
C, 69.30; H, 9.00; N, 1.92; found: C, 69.11; H, 9.24; N, 1.68.
Methyl 3b 3-(O-methyl-L-glutamyl)-11-oxo-olean-12-en-
30-oate (13)
Obtained from 11 (320 mg, 0.44 mmol) by method B as a color-
less powder; yield: 260 mg, 94%; mp 288–2908C (dec.); RF ¼ 0.73
(dichloromethane/methanol 9:1); [a]D ¼ 123.608 (c ¼ 0.54, meth-
anol); UV-VIS (methanol): lmax (log e) ¼ 250 nm (4.13); IR (KBr):
n ¼ 3259 (br), 2956 (s), 1724 (s), 1652 (s), 1582 (w), 1466 (m), 1389
(m), 1365 (m), 1322 (w), 1233 (s), 1164 (m), 1105 (m), 1022 (w), 982
(m), 919 (w), 850 (w), 750 (w), 682 (w), 589 (w), 541 (w) cmꢂ1
;
1H-NMR (400 MHz, CDCl3): d ¼ 5.66 (s, 1H, H-12), 4.56 (dd, 1H,
H-3, J ¼ 11.8, 4.7 Hz), 3.67 (s, 3H, Glu-OMe), 3.66 (s, 3H, OMe), 3.43
(dd, 1H, Glu-CHN, J ¼ 8.4, 4.7 Hz), 2.80 (ddd, 1H, H-1, J ¼ 13.7,
3.3, 3.3 Hz), 2.47 (dd, 2H, Glu-CH2COOMe, J ¼ 7.6, 7.2 Hz), 2.34
(s, 1H, H-9), 2.11 (m, 1H, Glu-CHH’CHN), 2.06 (m, 1H, H-18), 2.01
(m, 1H, H-15), 1.97 (m, 1H, H-21), 1.90 (ddd, 1H, H-19, J ¼ 13.7, 3.3,
2.5 Hz), 1.83 (m, 1H, Glu-CHH’CHN), 1.79 (m, 1H, H-16), 1.70
(m, 1H, H-2), 1.65 (m, 1H, H-7), 1.61 (m, 1H, H-2’), 1.59 (dd, 1H,
H-19’, J ¼ 13.3, 13.3 Hz), 1.55 (m, 1H, H-6), 1.45 (m, 1H, H-6’), 1.40
(m, 1H, H-7’), 1.35 (m, 1H, H-22), 1.34 (s, 3H, H-27), 1.29 (m, 2H,
H-22’ and H-21’), 1.16 (m, 1H, H-16’), 1.14 (s, 3H, H-25), 1.13 (s, 3H,
H-29), 1.11 (s, 3H, H-26), 1.04 (m, 1H, H-1’), 0.99 (m, 1H, H-15’), 0.88
(s, 3H, H-24), 0.86 (s, 3H, H-23), 0.80 (m, 1H, H-5), 0.78 (s, 3H, H-28)
ppm; 13C-NMR (125 MHz, CDCl3): d ¼ 200.0 (C-11), 176.9 (C-30),
173.6 (Glu-COOMe), 171.6 (Glu-COO), 169.2 (C-13), 128.5 (C-12),
81.5 (C-3), 61.7 (C-9), 55.0 (C-5), 54.1 (Glu-CHNH), 51.7 (OMe),
51.6 (Glu-OMe), 48.4 (C-18), 45.4 (C-8), 44.0 (C-20), 43.2 (C-14),
41.1 (C-19), 38.7 (C-1), 38.1 (C-4), 37.7 (C-22), 36.9 (C-10), 32.7
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