Table 3.
1H NMR assignments (500 MHz, CDCl3) of saquayamycins A (7), J (4), K (5) and B1 (6), δ in ppm relative to TMS (multiplicity, J/Hz).
| Position | Saquayamycin A (7)a) | Saquayamycin J (4)a) | Saquayamycin K (5)a) | Saquayamycin B1 (6)a) |
|---|---|---|---|---|
|
| ||||
| δH | δH | δH | δH | |
| 2 | 2.47, d (13.5, Ha), 3.13, dd (13.5, 2.5, He) | 2.47, d (13.0, Ha), 3.16, dd (13.0, 3.0, He) | 2.49, d (13.5, Ha), 3.16, dd (13.5, 3.0, He) | 2.60, d (13.5, Ha), 2.93, dd (12.5, 2.5, He) |
| 3-CH3 | 1.36, s | 1.38, s | 1.38, s | 1.27, s |
| 3-OH | - | - | - | 3.90, brs b) |
| 4 | 1.81, d (15.0, Ha), 2.24, dd (15.5, 3.0, He) | 1.81, d (15.5, Ha), 2.24, dd (15.0, 2.5, He) | 1.82, d (15.5, Ha), 2.26, dd (15.5, 3.0, He) | 1.82, d (15.0, Ha) 2.25, dd (14.0, 2.0, He) |
| 4a-OH | 4.30, brs | 4.38, brs | 4.31, brs | 3.54, brs b) |
| 5 | 6.40, d (10.0) | 6.42, d (10.0) | 6.42, d (10.0) | 6.38, d (10.0) |
| 6 | 6.86, d (9.5) | 6.87, d (9.5) | 6.89, d (10.0) | 6.87, d (9.5) |
| 8-OH | 12.25, s | 12.27, s | 12.26, s | 12.26, s |
| 10 | 7.83, d (8.0) | 7.85, d (8.0) | 7.85, d (8.0) | 7.87, d (7.5) |
| 11 | 7.56, d (7.5) | 7.57, d (8.0) | 7.58, d (7.5) | 7.59, d (8.0) |
| 12b-OH | 4.56, brs | 4.56, brs | 4.57, brs | 4.98, brs b) |
| Sugar A, β-D-olivose | ||||
| 1A | 4.84, brd (11.0) | 4.93, brd (9.5) | 4.84, brd (10.0) | 4.94, brd (10.0) |
| 2A | 1.45, m (Ha), 2.48, m (He) | 1.41, m (Ha), 2.41, ddd, 12.5, 4.5, 2.0, He) | 1.33 m (Ha), 2.49 m (He) | 1.40, m (Ha), 2.42, ddd (12.5, 4.5, 2.0, He) |
| 3A | 3.86, m | 3.78, m | 3.79, m | 3.79, m |
| 3A-OH | 4.23, brs | - | 3.46, brs | - |
| 4A | 3.17, dd (9.0, 8.5) | 3.45, dd (9.0, 9.0) | 3.01, dd (8.5, 8.5) | 3.46, dd (9.0, 9.0) |
| 5A | 3.53, m | 3.54, m | 3.53, m | 3.55, m |
| 6A | 1.35, d (6.0) | 1.37, d (6.0) | 1.33, d (6.5) | 1.38, d (6.0) |
| Sugar B, α-L-aculose or α-L-cinerulose or α-L-rhodinose | ||||
| 1B | 5.34, d (3.5) | 5.15, d (3.0) | 4.87, brs | 5.16, d (3.0) |
| 2B | 6.81, dd (10.0, 3.5) | 4.31, brm | 1.90–1.80, m (Ha, He) | 4.32, brq (3.0) |
| 3B | 6.10, d (10.5) | 2.60, dd (17.5, 3.0, Ha), 2.65, dd (17.5, 3.5, He) | 1.20, m (Ha), 1.90, m (He) | 2.60, dd (16.5, 3.0, Ha), 2.66, dd (17.5, 3.5, He) |
| 4B | - | - | 3.32, brm | - |
| 4B-OH | - | - | 4.93, brs | - |
| 5B | 4.72, q (6.5) | 4.69, q (7.0) | 3.84, m | 4.70, q (7.0) |
| 6B | 1.39, d (7.0) | 1.34, d (7.0) | 1.29, d (6.0) | 1.35, d (6.5) |
| Sugar C, α-L-rhodinose | ||||
| 1C | 5.21, brs | 5.23, brd (2.5) | 5.23, brs | - |
| 2C | 1.45, m (Ha), 1.88, m (He) | 1.42, m (Ha), 1.80, m (He) | 1.45, m (Ha), 1.90, m (He) | - |
| 3C | 1.99–1.88, m (Ha, He) | 1.76, m (Ha, He) | 2.01–1.90, m (Ha, He) | - |
| 4C | 3.65, brs | 3.54, brm | 3.67, brs | - |
| 5C | 4.18, m | 4.15, m | 4.22, m | - |
| 6C | 1.24, d (6.0) | 1.20, d (6.0) | 1.26, d (7.0) | - |
| Sugar D, α-L-aculose or α-L-rhodinose | ||||
| 1D | 5.22, d (3.5) | 4.76, brd (2.5) | 5.24, d (3.5) | - |
| 2D | 6.85, dd (9.5, 3.5) | 1.70, m (Ha), 1.95, m (He) | 6.86, dd (10.0, 3.5) | - |
| 3D | 6.04, d (10.0) | 1.80, m (Ha, He) | 6.07, d (10.5) | - |
| 4D | - | 3.26, brm | - | - |
| 4D-OH | - | 5.27, brs | - | - |
| 5D | 4.50, q (7.0) | 3.61, m | 4.52, q (6.5) | - |
| 6D | 1.32, d (7.0) | 1.21, d (6.0) | 1.34, d (7.0) | - |
a)
See also Figures S32–37, S40–45 and S48–59,
b)
Assignments may be interchangeable among the signals.