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A. A. Mar et al. / Bioorg. Med. Chem. Lett. 20 (2010) 5389–5393
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Necrotic Viable Apoptotic
Untreated DMSO
1
5b
5c
6a
6b
6c
8a
8c
8d
9b
Compound
Figure 1. Annexin assay: SK-MEL-2 cells were treated with 7.5
lM of test compounds for 16 h (error bars representing standard deviations of three replicates).
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11a
11b
11c
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11f
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Figure 2. Annexin assay: SK-MEL-2 cells were treated with 7.5
lM of test compounds for 16 h (error bars representing standard deviations of three replicates).
11. (a) Sharpless, K. B.; Lauer, R. F. J. Org. Chem. 1974, 39, 429; (b) Engman, L. J. Org.
death predominantly via apoptosis. The mono(aza) derivatives (5,
6, 8, 9, and 10) apparently triggered cell death via different, non-
apoptotic pathway(s). Further studies to elucidate the mechanism
of action by these aza-lupane triterpenoids are currently underway
and will be reported in due course.
Chem. 1987, 52, 4086.
12. The newly synthesized compounds provided satisfactory MS and NMR
(500 MHz, DMSO-d6) spectra without exhibiting any discernible impurities.
For the 3-amino compound (5, 6, 8 and 11), the stereochemistry at C3 is yet to
be determined. The selected analytical data of representative compounds are
shown as follows. Compound 5c: mp 204–210 °C. 1H NMR d 0.60 (s, 3H), 0.66
(d, J = 10.4 Hz, 1H), 0.78–0.98 (m, 2H), 0.75 (s, 3H), 0.86 (s, 6H), 0.93 (s, 3H),
1.06–1.54 (m, 15H), 1.56–1.68 (m, 3H), 1.64 (s, 3H), 1.75–1.90 (m, 3H), 2.11 (d,
J = 8.4 Hz, 1H), 2.22 (t, J = 9.2 Hz, 1H), 2.55 (m, 2H), 2.80–3.00 (m, 2H), 4.56 (s,
1H), 4.68 (s, 1H), 6.64 (d, J = 8.4 Hz, 2H), 6.98 (d, J = 8.4 Hz, 2H), 9.10 (br s, 1H).
MS (APCI+) m/e 577 (M+H); Compound 6a: mp 156–163 °C. 1H NMR d 0.62 (s,
3H), 0.75 (s, 3H), 0.78–1.08 (m, 5H), 0.86 (s, 3H), 0.93 (s, 3H), 0.98 (s, 3H), 1.10–
1.38 (m, 10H), 1.45–1.68 (m, 6H), 1.63 (s, 3H), 1.82–1.92 (m, 4H), 2.12 (dd,
J = 5.3, 13.1 Hz, 1H), 2.38 (m, 1H), 3.08, 3.52 (d-AB Type, J = 4.4 Hz,
JAB = 10.6 Hz, 2H), 4.21 (t, J = 5.0 Hz, 1H), 4.54 (d, J = 1.0 Hz, 1H), 4.66 (d,
J = 2.0 Hz, 1H). MS (ESI+) m/e 442 (M+H). Compound 8c: mp 240–247 °C. 1H
NMR d 0.60 (s, 3H), 0.66 (d, J = 11.0 Hz, 1H), 0.75 (s, 3H), 0.79–1.01 (m, 4H),
0.87 (s, 3H), 0.92 (s, 3H), 0.98 (s, 3H), 1.02–1.39 (m, 11H), 1.46 (d, J = 8.5 Hz,
1H), 1.54–1.70 (m, 5H), 1.80–2.01 (m, 4H), 2.22 (m, 1H), 2.50–2.60 (m, 2H),
2.87 (m, 1H), 3.05, 3.50 (d-AB Type, J = 5.4 Hz, JAB = 10.4 Hz, 2H), 3.88 (br s, 2H),
4.20 (t, J = 5.3 Hz, 1H), 4.71 (t, J = 5.5 Hz, 1H), 4.74 (s, 1H), 4.84 (s, 1H), 6.64 (d,
J = 8.0 Hz, 2H), 6.98 (d, J = 8.5 Hz, 2H), 9.09 (s, 1H). MS (APCI+) m/e 578 (M+H).
Compound 9b: mp 173–182 °C. 1H NMR (500 MHz, DMSO-d6) d 0.82–1.12 (m,
3H), 0.85 (s, 3H), 0.93 (s, 3H), 0.94 (s, 3H), 0.99 (s, 3H), 1.01 (s, 3H), 1.14–1.28
(m, 3H), 1.30–1.46 (m, 9H), 1.56–1.72 (m, 4H), 1.76–2.00 (m, 4H), 2.26–2.46
(m, 3H), 2.58 (m, 2H), 2.64 (m, 2H), 3.07 (m, 3H), 3.52 (dd, J = 4.7, 10.2 Hz, 1H),
4.20 (t, J = 5.0 Hz, 1H), 4.75 (s, 2H), 6.65 (dd, J = 2.0, 6.5 Hz, 2H), 6.97 (d,
J = 8.5 Hz, 2H), 9.10 (s, 1H). MS (APCI+) m/e 576 (M+). Compound 11a: mp 190–
References and notes
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