Table 1.
NMR Data of Bouillomide A (1) in DMSO-d6 a
| unit | position | δC, typeb | δH, mult. (J in Hz) | COSY | HMBC (H to C)c | ROESYc |
|---|---|---|---|---|---|---|
| Val-1 | 1 | 171.9, qC | - | - | - | - |
| 2 | 56.1, CH | 4.63, m | 3, NH | 1 | 3, 4, 5, NH | |
| 3 | 30.7, CH | 2.06, m | 2, 4, 5 | 1 | 2, 4, 5 | |
| 4 | 19.2, CH3 | 0.86, d (7.0) | 3 | 2, 3, 5 | 2, 3, 5, 4(Thr) | |
| 5 | 17.4, CH3 | 0.74, d (7.0) | 3 | 2, 3, 4 | 2, 3, 4, 4(Thr) | |
| NH | - | 7.52, d (8.0) | 2 | 2, 2(N-Me-Tyr) | ||
| N-Me-Tyr | 1 | 169.4, qC | - | - | - | - |
| 2 | 60.8, CH | 4.87, dd (11.5, 2.0) | 3a, 3b | 1 | 3a, NH(Val-1), 2(Phe) | |
| 3a | 32.8, CH2 | 3.08, dd (14.0, 12.0) | 2 | 4, 5/9 | 2, 3b, 5/9 | |
| 3b | 2.70, dd (12.0, 2.0) | 2 | 4, 5/9 | 3a, 5/9 | ||
| 4 | 127.3, qC | - | - | - | - | |
| 5/9 | 130.4, CH | 6.97, d (8.5) | 6/8 | 3a, 3b, 6/8, 7 | 6/8, 2(Phe) | |
| 6/8 | 115.3, CH | 6.76, d (8.5) | 5/9 | 4, 7 | 5/9 | |
| 7 | 156.4, qC | - | - | - | - | |
| N-Me | 30.4, CH3 | 2.74, s | 2, 1(Phe) | |||
| Phe | 1 | 170.5, qC | - | - | - | - |
| 2 | 50.2, CH | 4.72, dd (11.5, 4.5) | 3a, 3b | 1, 2(Ahp), 6(Ahp) | 3b, 2(N-Me-Tyr), 5/9(N-Me-Tyr) | |
| 3a | 35.3, CH2 | 2.86, dd (14.0, 12.0) | 2, 3b | 4, 5/9 | 3b, 5/9, 6(Ahp) 5(Ahp) | |
| 3b | 1.81, dd (14.0, 3.0) | 2, 3a | 4, 5/9 | 2, 3a, 5/9 | ||
| 4 | 136.7, qC | - | - | - | - | |
| 5/9 | 129.4, CH | 6.82, d (7.0) | 6/8 | 3a, 3b, 7 | 3a, 3b, 6/8, 5b (Ahp), 6(Ahp) | |
| 6/8 | 127.8, CH | 7.14, t (7.5) | 5/9, 7 | 4, 7 | 5/9 | |
| 7 | 126.2, CH | 7.14, t (7.5) | 6/8 | 4, 5/9 | ||
| Ahp | 2 | 168.7, qC | - | - | - | - |
| 3 | 48.2, CH | 3.77, m | 4a, 4b, NH | 2 | 5b, NH | |
| 4a | 21.9, CH2 | 2.40, m | 3, 4b, 5a | 4b, NH | ||
| 4b | 1.56, m | 3, 4a, | 4a, 5a, NH | |||
| 5a | 29.4, CH2 | 1.71, m | 4a, 5b, 6 | 4b, 5b, 6 | ||
| 5b | 1.52, m | 5a, 6 | 3, 5a, 6, 5/9 (Phe) | |||
| 6 | 73.7, CH | 5.06, s | 5a, 5b, OH | 2, OH | 5a, 5b, OH, 3a(Phe), 5/9(Phe) | |
| NH | - | 7.19, m | 3 | 3, 4a, 4b, NH(Abu) | ||
| OH | - | 6.20, br s | 6 | 6 | ||
| Abu | 1 | 165.8, qC | - | - | - | - |
| 2 | 130.1, qC | - | - | - | - | |
| 3 | 131.6, CH | 6.49, q (7.0) | 4 | 1, 4 | 4 | |
| 4 | 13.1, CH3 | 1.47, d (7.0) | 3 | 2, 3, 1(Thr) | 3, NH | |
| NH | - | 9.25, br s | 4, 2(Thr), 3(Thr), NH(Ahp) | |||
| Thr | 1 | 172.6, qC | - | - | - | - |
| 2 | 55.3, CH | 4.62, br s | NH | 3, 4, NH, NH(Abu) | ||
| 3 | 71.7, CH | 5.52, br s | 4 | 2, 4, NH, NH(Abu) | ||
| 4 | 18.0, CH3 | 1.21, d (6.5) | 3 | 2, 3 | 2, 3, 4(Val-1), 5(Val-1) | |
| NH | - | 7.93, d (6.5) | 2 | 2, 2(Val-2), 3(Val-2) | ||
| Val-2 | 1 | 171.8, qC | - | - | - | - |
| 2 | 57.1, CH | 4.36, t (7.0) | 3, NH | 1 | 3, 4, 5, NH(Thr) | |
| 3 | 30.7, CH | 2.04, m | 2, 4, 5 | 1 | 2, 4, 5, NH(Thr) | |
| 4 | 19.2, CH3 | 0.85, d (7.0) | 3 | 1, 2, 3 | 2, 3, 5 | |
| 5 | 17.7, CH3 | 0.80, d (7.0) | 3 | 1, 2, 3, 4 | 2, 3, 4, NH | |
| NH | - | 7.71, br s | 2 | 3, 5, 2(Ala) | ||
| Ala | 1 | 172.5, qC | - | - | - | - |
| 2 | 48.0, CH | 4.34, dd (7.5, 7.0) | 3, NH | 1, 3 | 3, NH (Val-2) | |
| 3 | 18.0, CH3 | 1.18, d (7.0) | 2 | 1, 2 | 2, NH | |
| NH | - | 8.03, d (7.5) | 2 | 2, 3, 1(Ba) | 2, 3, 2(Ba) | |
| Ba | 1 | 171.9, qC | - | - | - | - |
| 2 | 37.0, CH2 | 2.07, t (7.0) | 3 | 1, 3, 4 | 3, NH(Ala) | |
| 3 | 18.7, CH2 | 1.48, sxt (7.0) | 2, 4 | 1, 2, 4 | 2, 4 | |
| 4 | 13.1, CH3 | 0.83, t (7.0) | 3 | 2, 3 | 3 |
a
Measured at 500 MHz (1H) and 125 MHz (13C).
b
Determined from HSQC and/or HMBC spectra.
c
Refers to correlations on the same unit unless otherwise indicated.