Table 1.
1H NMR Data of 4A-Ketopremithramycin A2 (11), 4A-Keto-9-demethylpremithramycin A2 (12), 4C-Keto-demycarosylmithramycin (13), and 4E-Ketomithramycin (14) in Acetone-d6 at 400 MHz (δ in ppm Relative to Internal TMS)a
|
δ multiplicity (J/Hz)
|
||||
|---|---|---|---|---|
| 11 | 12 | 13 | 14c | |
| 2-H | 4.70 d (12) | |||
| 3-H | 2.78 br t (12) | 4.80 d (12) | ||
| 4-H | 4.24 s br | 4.31 s br | a: 2.92 dd (16)b e: 2.60 dd (16,3) |
2.82 br t (12) a: 3.00 complex |
| 4-OCH3 | 3.6 s | 3.61 d (1) | e: 2.68 dd (16,3) | |
| 4a-H | 3.13 ddd (11,4,3) | 3.13 ddd (11,4,3) | ||
| 5-H | a: 3.95 (16,4,1) e: 3.05 (16,3) |
3.96 d br (16) 3.07 obsc |
6.81 s | 6.86 s |
| 6-H | 6.97 d (1) | 7.03 s br | ||
| 7-H | 6.75 s | 6.69 s | ||
| 7-CH3 | 2.09 s | 2.15 s | ||
| 9-H | 6.45 s | |||
| 9-CH3 | 2.19 s | |||
| 10-H | 6.85 s | 6.84 s | ||
| 1′ | 4.88 d (1.5) | 4.88 d (2) | ||
| 1′-OCH3 | 3.40 s | 3.44 s | ||
| 2′ | 2.65 s | 2.64 s | ||
| 3′ | 4.24 d (3)b | 4.30 d (3)b | ||
| 4′ | 4.23 dq (6.5,3)b | 4.30 dq (6,3)b | ||
| 5′ | 1.22 d (6.5) | 1.27 d (6) | ||
| 1A | 4.94 dd (10,2) | 4.95 dd (10,2) | 5.34 dd (10,2) | 5.33 dd (10,2) |
| 2Aa | 1.86 ddd (12,12,10) | 1.85 ddd (12,12,10) | 1.80 ddd (12,12,10) | 1.85 ddd (12,12,10) |
| 2Ae | 2.45 m br | 2.44 ddd (12,5,2,) | 2.43 ddd (12,5,2)b | 2.40 ddd (12,5,2)b |
| 3A | 3.70 dd (12,5)b | 3.71 dd (12,5)b | 3.81b | 3.70b |
| 4A | 3.06 dd (9,9) | 3.06 dd (9,9) | ||
| 5A | 3.45 q (6) | 3.44 q (6)b | 3.52 dq (9,6) | 3.51 dq (9,6) |
| 5A-CH3 | 1.25 d (6) | 1.25 d (6) | 1.26 d (6) | 1.30 d (6) |
| 1B | 4.68 dd (10,2) | 4.69 dd (10,2) | 4.74 dd (10,2) | 4.72 dd (10,2) |
| 2B | 1.70 ddd (12,12,10) 1.90 ddd (12,5,2) |
1.73 ddd (12,12,10) 1.92 ddd (12,5,2) |
a: 1.55 ddd (12,12,10) e: 2.19 ddd (12,5,2) |
1.58 ddd (12,12,10) 2.20 ddd (12,5,2) |
| 3B | 3.82 ddd (12,5,3) | 3.83 mb | 3.6 ddd (12,9,5) | 3.60 ddd (12,9,5) |
| 4B | 3.52 s br | 3.50 s br | 2.99 dd (9,9) | 3.01 dd (9,9) |
| 5B | 3.70 q (6.5) | 3.70 q (6.5) | 3.40 dq (9,6) | 3.41 dq (9,6) |
| 5B-CH3 | 1.25 d (6.5) | 1.25 d (6.5) | 1.26 d (6) | 1.30 d (6) |
| 1C | 5.09 dd (10,2) | 5.14 dd (10,2) | ||
| 2Ca | 1.88 ddd (12,12,10) | 1.62 ddd (12,12,10) | ||
| 2Ce | 2.42 ddd (12,5,2)b | 2.55 ddd (12,5,2) | ||
| 3C | 3.84 dd (12,5) | 3.70 complex | ||
| 4C | 3.02 dd (9,9) | |||
| 5C | 3.40 q (6) | 3.32 dq (9,6) | ||
| 5C-CH3 | 1.26 d (6) | 1.30 d (6) | ||
| 1D | 4.74 dd (10,2) | 4.7 dd (10,2) | ||
| 2Da | 1.80 ddd (12,12,10) | 1.76 ddd (12,12,10) | ||
| 2De | 1.98 ddd (12,5,2) | 1.93 ddd (12,5,2) | ||
| 3D | 3.81 ddd (12,5,3)b | 3.82 complex | ||
| 4D | 3.56 s br | 3.54 s br | ||
| 5D | 3.70 q br (6.5) | 3.74 q (6) | ||
| 5D-CH3 | 1.26 d (6.5) | 1.24 d (6) | ||
a
br = broad; obsc = obscured by solvent or water; OH signals not visible due to 5% water in the samples.
b
Complex, partially overlapped by other signal(s).
c
Sugar E signals: 1-E, 5.42 dd (10,2); 2-Ea, 1.98 dd (14,10); 2-Ee, 2.30 dd (14,2); 3-E-CH3, 1.31 s; 5-E, 4.66 q (6); 5E-CH3, 1.30 d (6).