Table 1.
NMR data for milnamides E, F, and G (1–3) recorded in DMSO-d6 a at 30 °C.
| Position | 1 a | 2 b | 3 b | |||||||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| δC e | δH (J in Hz) e | ROESY e | gHMBCAD e | δC e,f | δH (J in Hz) e | ROESY e | gHMBCAD e | δC e | δH (J in Hz) e | ROESY e | gHMBCAD e | |||||||||||
| 1 | 48.6 | 3.62, d (14.4) 3.88, d (14.4) |
9 19 |
3, 4a, 9a 3, 4a, 9a, 19 |
160.9 | 156.8 | 9.14, s | 9, 19 | 3, 4a, 9a, 19 | |||||||||||||
| 3 | 72.1 | 3.40, s | 11, 19, 20, 20′ | 1, 4, 4a, 10, 19, 20 | 72.5 | 4.26, s | 11, 19, 20, 20′ | 1, 4, 4a, 10, 19, 20 | 72.2 | 4.80, s | 11, 19, 20, 20′ | 1, 4, 4a, 10, 19, 20 | ||||||||||
| 4 | 34.7 | 35.1 | 36.6 | |||||||||||||||||||
| 4a | 113.0 | 121.9 | 128.8 | |||||||||||||||||||
| 4b | 125.4 | 123.8 | 122.6 | |||||||||||||||||||
| 5 | 118.6 | 7.47, d (8.4) | 20′ | 4a, 4b, 7, 8a | 120.3 | 7.61, d (7.8) | 20′ | 7, 8a | 122.2 | 7.80, d (8.4) | 20′ | 7, 8a | ||||||||||
| 6 | 117.9 | 6.87, t (7.8) | 4b, 8 | 118.9 | 6.97, t (7.8) | 4b | 121.8 | 7.15, t (7.8) | 4b, 8 | |||||||||||||
| 7 | 119.5 | 6.95, t (7.8) | 5, 8a | 122.8 | 7.14, t (7.8) | 5, 8a | 128.3 | 7.43, t (7.8) | 5, 8a | |||||||||||||
| 8 | 110.9 | 7.24, d (8.4) | 9 | 4b, 6 | 112.3 | 7.36, d (7.8) | 9 | 4b | 113.8 | 7.54, d (8.4) | 9 | 4b, 6 | ||||||||||
| 8a | 135.9 | 137.0 | 141.4 | |||||||||||||||||||
| 9 | 10.62, s | 1, 8 | 4a, 4b, 8a, 9a | 11.46, s | 8 | 4a, 4b, 8a, 9a | 12.36, s | 1, 8 | 4a, 4b, 8a, 9a | |||||||||||||
| 9a | 131.8 | 125.6 | 124.1 | |||||||||||||||||||
| 10 | 169.7 | 168.7 | 163.9 | |||||||||||||||||||
| 11 | 7.90, d (9.6) | 3, 20′, 22 | 10 | 8.22, d (9.0) | 3, 20′, 22 | 10 | 8.64, d (9.0) | 3, 20′, 22 | 10 | |||||||||||||
| 12 | 53.4 | 4.75, d (9.0) | 22, 23 | 10, 12a, 13, 22 | 53.7 | 4.69, d (9.6) | 22, 23 | 12a, 22 | 55.0 | 4.64, d (9.0) | 22, 23 | 10, 12a, 13, 22 | ||||||||||
| 12a | 34.3 | 34.8 | 34.9 | |||||||||||||||||||
| 13 | 171.0 | 170.3 | 169.8 | |||||||||||||||||||
| 15 | 55.8 | 4.89, t (10.2) | 24, 24′, 25 | 13, 15a, 16, 17 | 55.8 | 4.85, t (10.2) | 24, 24′, 25 | 56.2 | 4.85, t (10.2) | 24, 24′, 25 | ||||||||||||
| 15a | 28.8 | 1.91, m | 16, 23 | 28.4 | 1.88, m | 16, 23 | 28.6 | 1.87, m | 16, 23 | |||||||||||||
| 16 | 138.2 | 6.59, d (9.6) | 15a, 23, 24 | 15a, 18, 25 | 138.0 | 6.59, dd (1.2, 10.2) | 15a, 23, 24 | 138.1 | 6.59, dd (1.2, 9.6) | 15a, 23, 24 | 18, 25 | |||||||||||
| 17 | 131.7 | 131.5 | 131.7 | |||||||||||||||||||
| 18 | 168.6 | 168.4 | 168.5 | |||||||||||||||||||
| 19 | 43.0 | 2.43, s | 1, 3, 22 | 1, 3, 9a | 32.6 | 2.86, s | 3, 22 | 1, 3 | 45.6 | 3.58, s | 1, 3, 22 | 1, 3 | ||||||||||
| 20 | 30.0 | 1.37, s | 3 | 3, 4, 4a, 20′ | 29.8 | 1.39, s | 3 | 3, 4, 4a, 20′ | 29.8 | 1.40, s | 3 | 3, 4, 4a, 20′ | ||||||||||
| 20′ | 24.1 | 1.30, s | 3, 5, 11 | 3, 4, 4a, 20 | 23.1 | 1.47, s | 3, 5, 11 | 3, 4, 4a, 20 | 22.1 | 1.61, s | 3, 5, 11 | 3, 4, 4a, 20 | ||||||||||
| 22 | 26.4 | 0.90, s | 11, 12, 19, 23, 25 | 12, 12a | 26.0 | 0.91, s | 11, 12, 19, 23, 25 | 12, 12a | 26.2 | 0.94, s | 11, 12, 19, 23 | 12, 12a | ||||||||||
| 23 | 30.8 | 2.87, s | 12, 15a, 16, 22, 24′ | 13, 15 | 30.7 | 2.81, s | 12, 15a, 16, 22, 24′ | 13, 15 | 31.0 | 2.82, s | 12, 15a, 16, 22, 24′ | 13, 15 | ||||||||||
| 24 | 19.3 | 0.77, d (6.6) | 15, 16, 24′ | 15, 15a, 24′ | 18.9 | 0.75, d (6.6) | 15, 16, 24′ | 15, 15a, 24′ | 19.2 | 0.73, d (6.6) | 15, 16, 24′ | 15, 15a, 24′ | ||||||||||
| 24′ | 18.8 | 0.68, d (6.6) | 15, 23, 24 | 15, 15a, 24 | 18.3 | 0.58, d (6.6) | 15, 23, 24 | 15, 15a, 24 | 18.5 | 0.51, d (6.6) | 15, 23, 24 | 15, 15a, 24 | ||||||||||
| 25 | 13.5 | 1.76, s | 15, 22 | 16, 17, 18 | 13.1 | 1.76, d (1.2) | 15, 22 | 16, 17, 18 | 13.3 | 1.77, d (1.2) | 16 | 16, 17, 18 | ||||||||||
| 18-OH | d | 12.40, brs | 12.43, brs | |||||||||||||||||||
a Compound in a FA form; b Compound in a TFA form; d Not determined; e1H NMR at 600 MHz referenced to residual DMSO solvent (δH 2.50 ppm) and 13C NMR at 150 MHz referenced to residual DMSO solvent (δC 39.52 ppm); f13C chemical shifts obtained from correlations observed in gHSQCAD and gHMBCAD spectra.