13C NMR spectrum (δ, ppm): 14.18 (q, C-27), 15.57 (q, C-25,26), 19.13 (q, C-30), 19.30 (t, C-6), 20.63 (q, C-24),
21.16 (t, C-11), 25.20 (t, C-37), 25.31 (t, C-12), 26.29 (q, C-23), 26.50 (t, C-33), 28.78, 28.70, 28.64 (t, C-34-36), 29.06 (t, C-
15), 29.40 (t, C-32), 30.54 (t, C-21), 33.34 (t, C-7,16), 33.58 (t, C-41), 33.74 (t, C-2), 34.54 (t, C-40), 36.16 (t, C-38), 36.56
(s, C-10), 37.38 (d, C-13), 38.05 (t, C-22), 38.78 (t, C-31), 39.28 (t, C-1), 40.36 (s, C-8), 42.16 (s, C-14), 46.33 (d, C-19), 46.90
(s, C-4), 49.66 (d, C-9 or C-18), 49.80 (d, C-18 or C-9), 51.27 (q, C-43), 54.86 (d, C-5), 55.18 (s, C-17), 108.92 (t, C-29),
150.56 (s, C-20), 172.44 (s, C-42), 172.62 (s, C-39), 175.70 (s, C-28), 217.60 (s, C-3).
N -{N-[3-Oxo-20(29)-lupen-28-oyl]-9-aminononanoyl}-3-amino-3-phenylpropionic Acid (5b). The reaction was
performed analogouslyusing 4d and β-alanine. An analyticallypure sample of5b was obtained bychromatographyover Al O
2
3
and drying in vacuum at 60°C over P O .
2
5
IR spectrum (ν, cm-1): 1669 (CONH), 1706 (C O), 1739 (COOMe).
PMR spectrum (δ, ppm, J/Hz): 0.84 (3H, s, Me-25), 0.90 (6H, s, Me-26,27), 0.93 (3H, s, Me-24), 0.94 (1H, m, H-12),
0.98 (3H, s, Me-23), 1.08 (1H, m, H-15), 1.18-1.45 (23H, m, H-1,5-7,9,11,15,16,21,22,32-36), 1.48 (1H, t, J = 11.3, H-18), 1.54
(2H, m, H-37), 1.60 (3H, s, Me-30), 1.64 (1H, m, H-12), 1.67 (1H, m, H-22), 1.78-1.91 (3H, m, H-1,16,21), 2.12 (1H, t, J = 7.4,
CH CONH), 2.31 and 2.39 (2H, both m, H-2), 2.47 (1H, ddd, J = 13.0, J = 11.3, J = 3.6, H-13), 2.74 and 2.83 (2H, ABX-
2
1
2
3
system with J = 15.6, J = 6.1 and J = 15.6, J = 6.4, CH COOMe), 3.06 (2H, m, H-19, CONHCH ), 3.17 (1H, m,
1
2
1
2
2
2
CONHCH ), 3.52 (3H, s, OMe), 4.51 and 4.65 (2H, both br.s, CH ), 5.36 (1H, dt, J = 8.5, J = 6.1, CHPh), 5.79 (1H, t,
2
2
1
2
J = 5.5, CONH), 6.75 (1H, d, J = 8.5, CONH), 7.14-7.25 (5H, m, Ph).
13C NMR spectrum (δ, ppm): 14.27 (q, C-27), 15.65 (q, C-25 or C-26), 15.70 (q, C-26 or C-25), 19.21 (q, C-30), 19.38
(t, C-6), 20.73 (q, C-24), 21.22 (t, C-11), 25.29 (t, C-37), 25.38 (t, C-12), 26.35 (q, C-23), 26.58 (t, C-33), 28.76, 28.79, 28.89
(t, C-34-36), 29.13 (t, C-15), 29.49 (t, C-32), 30.61 (t, C-21), 33.44 (t, C-7,16), 33.84 (t, C-2), 36.33 (t, C-38), 36.63 (s, C-10),
37.47 (d, C-13), 38.15 (t, C-22), 38.86 (t, C-31), 39.35 (t, C-1), 39.68 (t, C-41), 40.43 (s, C-8), 42.24 (s, C-14), 46.42 (d, C-19),
47.01 (s, C-4), 49.18 (d, C-40), 49.73 (d, C-9), 49.85 (d, C-18), 51.43 (q, C-43), 54.73 (d, C-5), 55.25 (s, C-17), 109.03 (t, C-
29), 125.98 (2C, d, Ph), 127.22 (d, Ph), 128.33 (2C, d, Ph), 140.53 (s, Ph), 150.64 (s, C-20), 171.27 (s, C-42), 172.09 (s, C-39),
175.73 (s, C-28), 217.81 (s, C-3).
Methyl Ester of N-[3-Hydroxyimino-20(29)-lupen-28-oyl]-9-amino Acid (6). A. A solution of 3d (0.20 g,
0.32 mmole) in alcohol (6.5 mL) was treated with hydroxylamine hydrochloride (0.05 g, 0.71 mmole) in pyridine (1.3 mL).
The reaction mixture was held at room temperature with periodic stirring for one day and poured onto a mixture of ice and HCl.
The precipitate was filtered off, washed with H O, and dried in a desiccator over P O .
2
2 5
IR spectrum (ν, cm-1): 1500, 1639, 1668, 1742 (COOMe).
PMR spectrum (δ, ppm, J/Hz): 0.85 (3H, s, Me-25), 0.87 (3H, s, Me-27), 0.89 (3H, s, Me-26), 0.91 (1H, m, H-12), 0.95
(1H, m, H-5), 0.96 (3H, s, Me-24), 1.06 (3H, s, Me-23), 1.07 (1H, m, H-15), 1.18-1.46 (21H, m, H-6,7,9,11,15,16,21,22,32-36),
1.47 (1H, t, J = 11.2, H-18), 1.54 (2H, m, H-37), 1.60 (3H, s, Me-30), 1.63 (1H, m, H-12), 1.68 (1H, m, H-22), 1.72 (1H, m,
H-1), 1.87 (2H, m, H-16,21), 2.15 (1H, m, H-2), 2.23 (1H, t, J = 7.6, CH COOMe), 2.42 (1H, ddd, J = 12.8, J = 11.6,
2
1
2
J = 3.4, H-13), 2.92 (1H, dt, J = 15.2, J = 4.6, H-2), 3.08 (2H, m, H-19, CONHCH ), 3.22 (1H, m, CONHCH ), 3.59 (3H,
3
1
2
2
2
s, OMe), 4.51 and 4.66 (2H, both br.s, CH ), 5.70 (1H, t, J = 5.6, CONH), 9.63 (1H, br.s, NOH).
2
B. Compound 3d (0.62 g, 1 mmole) in alcohol (20 mL) was treated with hydroxylamine hydrochloride (0.11 g,
1.57 mmole) and CH CO Na (0.21 g, 2.56 mmole). The reaction mixture was boiled for 7 h, cooled to room temperature, and
3
2
worked up as described above. The yield of 6 was 96%.
Methyl Ester of N-[3β-Hydroxy-20(29)-lupen-28-oyl]-9-amino Acid (7). A solution of 3d (0.50 g, 0.8 mmole) in
anhydrous THF (25 mL) at 0°C was vigorously stirred and treated in small portions with NaBH (0.5 g, 13.2 mmole). The
4
reaction mixture was held at room temperature for 5 h and poured onto a mixure of ice and dilute HCl. The precipitate was
filtered off, washed with H O, and dried in a vacuum desiccator over P O . An analytically pure sample of 7 was obtained by
2
2 5
chromatography over Al O and drying in vacuum at 60°C over P O .
2
3
2 5
IR spectrum (ν, cm-1): 1645 (C C), 1667 (CONH), 1741 (COOMe), 3467 (OH).
PMR spectrum (δ, ppm, J/Hz): 0.82 (3H, s, Me-24), 0.85 (3H, s, Me-25), 0.92 (3H, s, Me-26), 0.93 (6H, s, Me-23,27),
1.65 (3H, s, Me-30), 2.18 (2H, t, J = 7.6, CH COOMe), 2.43 (1H, ddd, J = 12.7, J = 11.5, J = 3.6, H-13), 3.27-3.02 (4H, m,
2
1
2
3
H-3,19, CONHCH ), 3.54 (3H, s, OMe), 4.46 and 4.61 (2H, both br.s, CH ), 5.78 (1H, t, J = 5.7, CONH) (only characteristic
2
2
signals are given).
3β-Acetoxy-20(29)-lupen-28-oic Acid (9). A mixture of pure betulin (4.42 g, 10 mmole) and acetic anhydride
(15 mL) was boiled for 1 h and cooled to room temperature. The precipitate was filtered off, washed with H O, and dried in
2
337