1
3ꢁ,28-Diacetoxy-30-(4-hydroxymethyl-1,2,3-triazol-1-yl)lup-20(29)-ene (7). Í NMR spectrum (ꢆ, ppm, J/Hz):
0.75 (1Í, d, J = 9.4, Í-5), 0.80 (3Í, s, Ìå-25), 0.81 (6Í, s, Ìå-23, 24), 0.93 (3Í, s, Ìå-27), 0.96 (1Í, m, Í-1), 0.98 (3Í, s,
Ìå-26), 1.09–1.11 (3Í, m, Í-12, 15, 22), 1.16 (1Í, m, Í-11), 1.20–1.29 (4Í, m, Í-9, 15, 16, 21), 1.32–1.40 (4Í, m, Í-6, 7,
7, 11), 1.47 (1Í, m, Í-6), 1.54–1.69 (6Í, m, Í-1, 2, 2, 12, 13, 18), 1.74 (1Í, m, Í-22), 1.80 (1Í, m, Í-16), 1.94 (1Í, m,
Í-21), 2.00 (3Í, s, Me-32), 2.02 (3Í, s, Me-34), 2.30 (1Í, m, Í-19), 3.72 (1Í, d, J = 11.0, Í-28), 4.19 (1Í, d, J = 11.0, Í-28),
4.43 (1Í, dd, J = 10.9, J = 5.3, Í-3), 4.60 (1Í, s, Í-29), 4.76 (2Í, s, ÑÍ ÎÍ), 4.89 (2Í, ÀÂ-system, J = 15.5, Í-30, 30),
1
2
2
gem
4.99 (1Í, s, Í-29), 7.50 (1Í, s, Í-5ꢀ).
1
3ꢁ,28-Diacetoxy-30-(4-phenyl-1,2,3-triazol-1-yl)lup-20(29)-ene (8). Í NMR spectrum (ꢆ, ppm, J/Hz): 0.75 (1Í,
d, J = 9.4, Í-5), 0.81 (6Í, s, 2Ìå), 0.82 (3Í, s, Ìå), 0.92 (3Í, s, Ìå), 0.99 (3Í, s, Ìå), 1.73 (1Í, t, J = 11.1, Í-18), 2.02 (3Í,
s, Ìå-34), 2.03 (3Í, s, Ìå-32), 2.36 (1Í, td, J = 10.5, J = 5.1, Í-19), 3.73 (1Í, d, J = 11.0, Í-28), 4.22 (1Í, d, J = 11.0,
1
2
Í-28), 4.44 (1Í, dd, J = 11.3, J = 5.6, Í-3), 4.71 (1Í, s, Í-29), 4.97 (2Í, ÀÂ-system, J = 15.5, Í-30, 30), 5.04 (1Í, s,
1
2
gem
Í-29), 7.31 (1Í, t, J = 7.4, Í-9ꢀ), 7.40 (2Í, t, J = 7.8, Í-8ꢀ, 10ꢀ), 7.72 (1Í, s, Í-5ꢀ), 7.81 (2Í, d, J = 8.7, Í-7ꢀ, 11ꢀ) (only
characteristic proton resonances are given).
1
3ꢁ,28-Diacetoxy-30-(4-pyridyl-1,2,3-triazol-1-yl)lup-20(29)-ene (9). Í NMR spectrum (ꢆ, ppm, J/Hz): 0.73 (1Í,
d, J = 9.9, Í-5), 0.80 (3Í, s, Ìå-24), 0.81 (6Í, s, Ìå-23, 25), 0.92 (1Í, m, Í-1), 0.93 (3Í, s, Me-27), 0.99 (3Í, s, Ìå-26),
1.02–1.17 (4Í, m, Í-11, 12, 15, 22), 1.20–1.25 (2Í, m, Í-9, 16), 1.26–1.44 (6Í, m, Í-6, 7, 7, 11, 15, 21), 1.46 (1Í, m, Í-6),
1.53–1.66 (5Í, m, Í-1, 2, 2, 12, 13), 1.71 (1Í, t, J = 11.2, Í-18), 1.74 (1Í, m, Í-22), 1.80 (1H, m, Í-16), 1.97 (1Í, m, Í-21),
2.01 (3Í, s, Ìå-34), 2.02 (3Í, s, Ìå-32), 2.37 (1Í, td, J = 10.5, J = 5.2, Í-19), 3.73 (1Í, d, J = 11.1, Í-28), 4.21 (1Í, d,
1
2
J = 11.0, Í-28), 4.44 (1Í, dd, J = 11.1, J = 6.3, Í-3), 4.68 (1Í, s, Í-29), 4.96 (2Í, AB-system, J = 15.6, Í-30, 30), 5.03
1
2
gem
(1Í, s, Í-29), 7.20 (1Í, ddd, J = 7.9, J = 4.8, J = 1.2, Í-9ꢀ), 7.76 (1Í, td, J = 7.7, J = 1.8, Í-10ꢀ), 8.11 (1Í, s, Í-5ꢀ), 8.16
1
2
3
1
2
(1Í, dt, J = 8.0, J = 1.0, Í-11ꢀ), 8.55 (2Í, dq, J = 4.82, J = 1.8, J = 1.0, Í-8ꢀ).
1
2
1
2
3
1
3ꢁ-Acetoxy-30-(4-hydroxymethyl-1,2,3-triazol-1-yl)lup-20(29)-en-28-oic Acid Methyl Ester (10).
Í NMR
spectrum (ꢆ, ppm, J/Hz): 0.75 (1Í, d, J = 8.8, Í-5), 0.80 (3Í, s, Me), 0.81 (6Í, s, 2Ìå), 0.86 (3Í, s, Ìå), 0.92 (3Í, s, Ìå),
1.66 (1H, t, J = 11.5, H-18), 1.82 (1H, dd, J = 12.0, J = 8.1, Í-22), 1.90 (1Í, m, Í-16), 2.01 (3Í, s, Me-32), 2.14 (1Í, td,
1
2
J = 12.7, J = 2.3, Í-13), 2.21 (1Í, m, Í-21), 2.91 (1Í, td, J = 11.2, J = 5.1, Í-19), 3.63 (3Í, s, ÎÌå), 4.44 (1Í, dd, J = 10.5,
1
2
1
2
1
J = 5.9, Í-3), 4.58 (1Í, s, Í-29), 4.78 (2Í, s, ÑÍ OH), 4.91 (2Í, ÀÂ-system, J = 15.7, Í-30, 30), 5.02 (1Í, s, Í-29), 7.52
2
2
gem
(1Í, s, Í-5ꢀ) (only characteristic proton resonances are given).
1
3ꢁ-Acetoxy-30-(4-phenyl-1,2,3-triazol-1-yl)lup-20(29)-en-28-oic Acid Methyl Ester (11). Í NMR spectrum
(ꢆ, ppm, J/Hz): 0.75 (1Í, d, J = 8.3, Í-5), 0.80 (3Í, s, Ìå), 0.81 (6Í, s, 2Ìå), 0.87 (3Í, s, Ìå), 0.92 (3Í, s, Ìå), 1.70 (1H,
t, J = 11.4, Í-18), 2.01 (3Í, s, Ìå-32), 2.96 (1Í, td, J = 10.8, J = 4.4, Í-19), 3.62 (3Í, s, ÎÌå), 4.44 (1Í, dd, J = 10.0,
1
2
1
J = 5.0, Í-3), 4.68 (1Í, s, Í-29), 4.96 (2Í, ÀÂ-system, J
= 16.3, Í-30, 30), 5.05 (1Í, s, Í-29), 7.30 (1Í, t, J = 7.4,
2
gem
1
Í-9ꢀ), 7.40 (2Í, t, J = 7.2, Í-8ꢀ, 10ꢀ), 7.73 (1Í, s, Í-5ꢀ), 7.81 (2Í, d, J = 7.0, Í-7ꢀ, 11ꢀ).
1
1
3ꢁ-Acetoxy-30-(4-pyridyl-1,2,3-triazol-1-yl)lup-20(29)-en-28-oic Acid Methyl Ester (12). Í NMR spectrum
(ꢆ, ppm, J/Hz): 0.75 (1Í, d, J = 8.9, Í-5), 0.80 (3Í, s, Ìå-24), 0.81 (6Í, s, Ìå-23, 25), 0.87 (3Í, s, Ìå-26), 0.92 (3Í, s,
Ìå-27), 0.94 (1Í, m, Í-1), 1.05 (1Í, m, Í-12), 1.13 (1Í, m, Í-15), 1.19–1.26 (2Í, m, Í-9, 11), 1.27–1.36 (5Í, m, Í-6, 7,
7, 15, 16), 1.39–1.48 (5Í, m, Í-6, 11, 12, 21, 22), 1.53–1.66 (3Í, m, Í-1, 2, 2), 1.69 (1Í, t, J = 11.3, H-18), 1.83 (1Í, dd,
J = 12.6, J = 8.1, Í-22), 1.92 (1Í, m, Í-16), 2.02 (3Í, s, Me-32), 2.16 (1Í, m, Í-13), 2.23 (1Í, m, Í-21), 2.98 (1Í, td,
1
2
J = 11.0, J = 4.6, Í-19), 3.63 (3Í, s, OÌå), 4.44 (1Í, dd, J = 10.5, J = 5.1, Í-3), 4.64 (1Í, s, Í-29), 4.98 (2Í, AB-system,
1
2
1
2
J
= 15.9, Í-30, 30), 5.05 (1Í, s, Í-29), 7.22 (1Í, ddd, J = 7.5, J = 5.1, J = 0.8, Í-9ꢀ), 7.78 (1Í, td, J = 7.8, J = 1.6,
gem
1 2 3 1 2
Í-10ꢀ), 8.16 (1Í, s, Í-5ꢀ), 8.19 (1Í, d, J = 7.8, Í-11ꢀ), 8.55 (1Í, dq, J = 4.8, J = 1.6, J = 0.8, Í-8ꢀ).
1
2
3
General Method for Alkaline Hydrolysis of 30-(1,2,3-triazol-1-yl)lupanes (7–12). A solution of triazole
(0.3 mmol) in a mixture of MeOH (10 mL) and THF (5 mL) under Ar at 0°C was treated with NaOH solution (0.37 mL, 4 N),
held at room temperature for 24 h, and poured out into a mixture of ice and HCl. The resulting precipitate was filtered off,
washed with H O, and dried in air. The obtained product was chromatographed over SiO (Acros, 0.035–0.070 mm) using a
2
2
mixture of CHCl and MeOH (20:1) as eluent. Compounds 13–18 were obtained as white precipitates; 13–16 were additionally
3
recrystallized from MeOH.
1
3ꢁ,28-Dihydroxy-30-(4-hydroxymethyl-1,2,3-triazol-1-yl)lup-20(29)-ene (13). Í NMR spectrum (ꢆ, ppm,
J/Hz): 0.75 (1Í, d, J = 8.8, Í-5), 0.81 (9Í, s, Ìå-23, 24, 25), 0.87 (3Í, s, Ìå-27), 0.96 (3Í, s, Ìå-26), 2.31 (1Í, m, Í-19),
3.15 (1Í, dd, J = 10.4, J = 4.6, Í-3), 3.24 (1Í, d, J = 11.1, Í-28), 3.73 (1Í, d, J = 11.1, Í-28), 4.70 (1Í, s, Í-29), 4.75 (2Í,
1
2
s, ÑÍ ÎÍ), 4.84 (2Í, ÀÂ-system, J
= 15.7, Í-30, 30), 5.04 (1Í, s, Í-29), 7.50 (1Í, s, Í-5ꢀ) (only characteristic proton
2
gem
resonances are given).
662