Table 2.
1H and 13C NMR data of 1, 10 and 11.
| # | 1 | 1 | 10 | 10 | 11 | 11 | ||
|---|---|---|---|---|---|---|---|---|
| 1H | 13C | 1H | 13C | HMBC | 1H | 13C | HMBC | |
| 1 | 4.44 m | 56.0 (d) | 5.98 d (4.3) | 49.4 | C-3, 4a, 9a, 10, 11, 14 |
5.08 d (10.0) | 52.2 | C-3, 4a, 9a, 10, 11, 14 |
| 3 | 3.31 brs 3.05 m |
40.8 (t) | 4.06 dd (2.0, 12.4), 3.42 m |
41.9 | C-14 | 4.98 dd (5.6, 11.6), 2.81 m** |
38.3 | - |
| 4 | 2.51 m | 16.0 (t) | 2.81 m | 21.8 | C-4a | 2.81 m** | 20.7 | C-4a |
| 4a | - | 109.6 (s) | - | 109.6 | - | - | 110.2 | - |
| 4b | - | 119.9 (s) | - | 120.4 | - | - | 120.0 | - |
| 5 | 6.90* | 118.0 (d) | 7.34 d (8.8) | 118.9 | C-4a, 4b, 7, 8a | 7.34 d (8.4) | 119.1 | C-4a, 4b, 7, 8a |
| 6 | 6.19 brd (8.8) | 108.3 (d) | 6.77 dd (2.0, 8.8) | 109.1 | C-4b, 7, 8 | 6.76 dd (2.4, 8.8) | 109.8 | C-4b, 7, 8 |
| 7 | - | 158.5 (s) | - | 156.8 | - | - | 156.9 | - |
| 8 | 6.35 d (2.8) | 94.6 (d) | 6.81 d (2.0) | 94.8 | C-4b, 6, 7, 8a | 6.92 d (2.4) | 95.2 | C-4b, 6, 7, 8a |
| 8a | - | 137.0 (s) | - | 137.2 | - | - | 137.1 | - |
| 9a | - | 120.0 (s) | - | 126.7 | - | - | 126.7 | - |
| 10 | 4.23 d brs | 73.0 (d) | 4.32 d (4.3) | 72.9 | C-1, 1´, 9a, 12 | 3.98 d (10.0) | 81.2 | C-1, 1´, 9a, 11, 12 |
| 11 | 4.44 m | 79.3 (d) | 5.20 d (8.4) | 77.2 | C-10, 12, 13 | 5.77 d (4.4) | 69.5 | C-10, 12, 13 |
| 12 | 4.09 brs | 68.9 (d) | 5.61 t (8.0,8.4) | 72.5 | C-10, 11, 13 | 5.32 t (4.4, 4.8) | 71.1 | C-10, 11, 13 |
| 13 | 4.04 brs | 70.9 (d) | 5.72 d (8.0) | 71.2 | C-12 | 5.87 d (4.8) | 73.4 | C-12, 14 |
| 14 | - | 175.3 (s) | - | 170.6 | - | - | 164.4 | |
| 1´ | 4.44 m | 94.4 (d) | 4.54 d (4.8) | 96.7 | C-2´, 10 | 4.91 d (3.6) | 101.6 | C-2´, 10 |
| 2´ | 4.36 m** | 71.8 (d) | 4.94–5.0 m** | 71.4 | - | 5.11–5.17 m** | 71.5 | - |
| 3´ | 4.38 m** | 71.7 (d) | 4.94–5.0 m** | 72.1 | - | 5.11–5.17 m** | 73.3 | - |
| 4´ | 4.31 m | 66.1 (d) | 4.94–5.0 m** | 68.6 | C-6´ | 5.11–5.17 m** | 67.4 | C-6´ |
| 5´ | 3.82 m** | 72.3 (d) | 3.55 m | 72.8 | - | 3.81 dd (2.4, xx) | 72.5 | - |
| 6´ | 3.81 m** 3.31 m |
61.5 (t) | 4.30 dd (5.2, 12.0), 4.12 m |
62.2 | C-4´ | 4.38 dd 4.0,12.4), 4.0 dd (1.2, 12.4) |
61.5 | C-4´ |
| 7-OMe | 3.23 s | 54.3 q | 3.83 s | 55.6 q | C-7 | 3.86 s | 55.7 | C-7 |
| OH/NH | - | - | 8.45 s (NH) | - | C-4a, 4b, 8a, 9a |
7.9 brs (NH) | - | C-4a, 4b, 8a, 9a |
| OCOMe | - | - | 2.23, 2.15, 2.14, 2.07, 1.98, 1.94, 1.91 (7 × s) |
22.0, 20.7, 20.5 ×3, 20.4, 20.2 (7q) |
- | 2.21, 2.17, 2.09 × 2, 2.01, 2.0, 1.53, (7 × s) |
20.9,20.6, 20.6 ×3, 20.5 ×2 (7q) |
- |
| CO-Me | - | - | - | 170.7, 170.1, 169.9, 169.5, 169.4, 169.2 ×2 |
- | - | 170.4 ×2, 170.1, 170.0, 169.4 ×2, 169.2 |
- |
NMR Spectra of 1 (CF3COOD/D2O), and 10 and 11 (in CDCl3) were recorded at 400 (1H) and 100 (13C) MHz, using a Varian spectrometer. The coupling constants (J values, in Hz) are in parentheses. The multiplicities of carbon signals were determined by 13C NMR DEPT experiments. Assignments were made using 2D NMR COSY, HMBC and HMQC experiments.
*
Signals superimposed with solvent.
**
Signals superimposed on each other.