Table 2.
NMR spectroscopic data for pitipeptolides E (5) and F (6) in CDCl3 (δ in ppm, J in Hz) at 600 MHz
| Unit | C/H No. | Pitipeptolide E (5) | Pitipeptolide F (6) | ||||
|---|---|---|---|---|---|---|---|
| δ C | δH (J) | HMBC a | δ C | δH (J) | HMBC a | ||
| Dhoya | 1 | 175.2 qC | – | 2 (Val), 3, 9, 10, NH (Val) |
175.3 qC | – | 2 (Val), 3, 9, 19, NH (Val) |
| 2 | 45.2 qC | – | 3, 4, 9, 10 | 45.3 qC | – | 9, 10 | |
| 3 | 77.1 CH | 4.97 dd (9.3, 2.9) | 5, 9 | 77.2 CH | 4.95 dd (9.6, 2.0) | 1 (Gly), 1, 2, 4, 9, 10 | |
| 4 | 28.8 CH2 | 1.82 m 1.58 m |
3, 5 | 28.9 CH2 | 1.83 m 1.48 m |
3, 5, 6 | |
| 5 | 24.4 CH2 | 1.43 m | 3, 4, 6 | 24.4 CH2 | 1.43 m | 3, 4, 6 | |
| 6 | 18.1 CH2 | 2.22 m | 3, 5, 7 | 18.1 CH2 | 2.22 m | 5 | |
| 7 | 83.6 qC | – | 5, 6, 8 | 83.4 qC | – | 5, 6, 8 | |
| 8 | 69.3 CH | 1.97 t (2.6) | 6 | 69.4 CH | 1.96 t (2.6) | 6, 7 | |
| 9 | 19.4 CH3 | 1.30 s | 10 | 19.4 CH3 | 1.25 s | 3, 10 | |
| 10 | 23.0 CH3 | 1.16 s | 3, 5, 9 | 23.0 CH3 | 1.16 s | 3, 9 | |
| Val | 1 | 171.6 qC | – | 2, 3, NH, 10 (N-Me- Phe) |
171.7 qC | – | 2, 3, NH, 10 (N-Me- Phe) |
| 2 | 53.4 CH | 4.69 dd (9.6 , 1.8) | 3, 4, 5, NH | 53.5 CH | 4.70 dd (9.0, 1.4) | 4, 5, NH | |
| 3 | 29.5 CH | 1.76 m | 2, 4, 5 | 29.5 CH | 1.76 m | 2, 4, 5 | |
| 4 | 16.0 CH3 | 0.90 d* | 2, 3, 5 | 16.0 CH3 | 0.90 d (7.1) | 2, 3, 5 | |
| 5 | 20.3 CH3 | 0.89 d* | 2, 3, 4 | 20.5 CH3 | 0.89 d (6.9) | 2, 3, 4 | |
| NH | – | 6.06 d (8.9) | – | – | 6.09 d (9.0) | – | |
| N-Me-Phe | 1 | 172.3 qC | – | 2, 3 | 171.8 qC | – | 2 |
| 2 | 65.9 CH | 3.86 dd (11.6, 3.2) | 3, 10 | 65.9 CH | 3.85 dd (11.2, 3.4) | 3, 10 | |
| 3 | 33.9 CH2 | 3.21 dd (14.2, 3.5) 3.12 dd (14.2, 11.2) |
2, 5/9 | 34.0 CH2 | 3.21 dd (14.4, 3.3) 3.11 dd (14.4, 11.4) |
1, 2, 5/9 | |
| 4 | 137.3 qC | – | 2, 3, 6/8 | 137.3 qC | – | 2, 3, 6/8 | |
| 5/9 | 129.2 CH | 7.12 d (7.5) | 6/8, 7 | 129.4 CH | 7.10 d (7.2) | 6/8 | |
| 6/8 | 128.9 CH | 7.29 m | 5/9, 7 | 129.0 CH | 7.28 m | 5/6, 7 | |
| 7 | 127.2 CH | 7.24 m | 5/9, 6/8 | 127.3 CH | 7.24 m | 5/9, 6/8 | |
| 10 | 39.3 CH3 | 2.80 s | 2 | 39.3 CH3 | 2.78 s | 2 | |
| Hivab/Hmpac | 1 | 169.2 qC | – | 2 | 172.3 qC | – | 2 |
| 2 | 78.5 CH | 4.90 d (6.7) | 3, 4, 5 | 78.4 CH | 4.92 d (6.8) | 4, 6 | |
| 3 | 30.7 CH | 2.05 m | 2, 4, 5 | 37.3 CH | 1.81 m | 2, 5, 6 | |
| 4 | 18.2 CH2 | 0.98 d* | 2, 3, 5 | 24.9 CH2 | 1.15 m 1.58 m |
6 | |
| 5 | 18.2 CH2 | 0.98 d* | 2, 3, 4 | 11.7 CH3 | 0.89 t (8.1) | 4 | |
| 6 | – | – | – | 14.6 CH3 | 0.93 d (7.2) | 2, 3 | |
| Pro | 1 | 170.0 qC | – | 2, 3, NH (Ile) | 170.4 qC | – | 2, NH (Ile) |
| 2 | 61.2 CH | 4.62 d (7.8) | 3 | 61.3 CH | 4.62 d (6.5) | 3, 4, 5 | |
| 3 | 31.4 CH2 | 2.65 m 1.96 m |
2, 4, 5 | 31.4 CH2 | 2.64 m 1.97 m |
2, 4, 5 | |
| 4 | 21.8 CH2 | 1.97 m 1.76 m |
2, 3, 5 | 21.8 CH2 | 1.98 m 1.77 m |
2, 3, 5 | |
| 5 | 46.5 CH2 | 3.70 m 3.55 dd (10.4, 10.2) |
2, 3, 4 | 46.5 CH2 | 3.70 m 3.56 dd (12.4, 9.7) |
2, 3, 4 | |
| Ileb/Valc | 1 | 171.4 qC | – | 2, 2 (Gly), NH (Gly) | 171.4 qC | – | 2, 2 (Gly), NH (Gly) |
| 2 | 61.1 CH | 4.20 dd (9.3, 8.5) | 3, 6, NH | 62.4 CH | 4.13 dd (9.8, 8.5) | 3, 4, 5, NH | |
| 3 | 35.2 CH | 2.04 m | 2, 4, 5, 6, NH | 29.2 CH | 2.24 m | 2, 4, 5 | |
| 4 | 25.9 CH2 | 1.58 m 1.24 m |
2, 5, 6 | 19.5 CH3 | 1.01 d (6.9) | 3, 5 | |
| 5 | 10.8 CH3 | 0.87 t (7.5) | 4 | 19.7 CH3 | 1.03 d (7.0) | 3, 4 | |
| 6 | 15.8 CH3 | 1.00 d (6.8) | 2, 3, 4 | – | – | – | |
| NH | – | 7.91 d (8.2) | – | – | 7.88 d (8.3) | – | |
| Gly | 1 | 169.9 qC | – | 2, 3 (Dhoya), NH | 169.9 qC | – | 2, 3 (Dhoya), NH |
| 2 | 41.0 CH2 | 4.62 dd (17.9, 8.7) 3.99 d (17.9) |
– | 41.2 CH2 | 4.62 dd (18.0, 9.4) 4.01 d (18.0) |
– | |
| NH | – | 6.39 d (9.3) | – | – | 6.40 d (9.0) | – | |
a
Protons showing long-range correlation to indicated carbon
b
Refers to compound 5
c
Refers to compound 6
*
Could not deduce coupling constants due to overlapping peaks