Table 2.
1H (400 MHz) and 13C (75.4 MHz) NMR Spectroscopic Data (pyridine-d5) of Demycarosyl-3C-β-d-mycarosyl-MTM (3) and 3A-Deolivosyl-MTM (4)
| 3 |
4 |
|||||||
|---|---|---|---|---|---|---|---|---|
| pos. | δC, mult. | δH (J in Hz) | HMBC | NOESY | δC | δH (J in Hz) | HMBC | NOESY |
| 1 | 204.2, qC | 204.4 | ||||||
| 2 | 77.9, CH | 4.96 d (11.6) | C-1, C-1C, C-3, C-4, C-1′ | H-1C, H-3, H-4ax, H-4eq | 77.9 | 4.96 d (11.6) | C-1, C-1C, C-3, C-4, C-1′ | H-1C, H-3, H-4ax, H-4eq |
| 3 | 42.6, CH | 3.48 m | C-2, C-4, C-1′ | H-2, H-4ax, H-4eq, H-1′ | 42.6 | 3.48 m | C-2, C-4, C-1′ | H-2, H-4ax, H-4eq, H-1′ |
| 4ax | 28.2, CH2 | 3.10 dd (15.9 and 3.6) | C-2, C-3, C-1′ | H-3, H-2 | 28.1 | 3.12 dd (15.9 and 3.6) | C-2, C-3, C-1′ | H-3, H-2 |
| 4eq | 3.27 dd (15.9 and 13.0) | H-3, H-2 | 3.26 dd (15.9 and 13.0) | H-3, H-2 | ||||
| 4a | 137.2, qC | 137.2 | ||||||
| 5 | 102.2, CH | 7.04 s | C-6, C-8a, C-7, C-10 | H-10, H-1A, H-5A | 102.2 | 7.04 s | C-6, C-7, C-8a, C-10 | H-10, H-1A, H-5A |
| 6 | 160.5, qC | 160.6 | ||||||
| 7 | 111.2, qC | 111.7 | ||||||
| 7-CH3 | 8.9, CH3 | 2.47 s | C-6, C-7, C-8 | 8.9 | 2.48 s | C-6, C-7, C-8 | ||
| 8 | 157.0, qC | 157.0 | ||||||
| 8a | 109.3, qC | 109.4 | ||||||
| 9 | 166.0, qC | 165.9 | ||||||
| 9a | 108.2, qC | 108.9 | ||||||
| 10 | 117.4, CH | 6.62 s | C-5, C-8a, C-9a, C-10a | H-5, H-1A, H-4ax, H-4eq | 117.4 | 6.62 s | C-5, C-8a, C-9a, C-10a | H-5, H-1A, H-4ax, H-4eq |
| 10a | 139.4, qC | 139.5 | ||||||
| 1′ | 83.0, CH | 5.49 d (1.2) | C-2, C-3, C-4, 1′-OCH3, C-2′ | H-2, H-3, 1′-OCH3 | 83.0 | 5.49 d (1.2) | C-2, C-3, C-4, 1′-OCH3, C-2′ | H-2, H-3, 1′-OCH3 |
| 1′-OCH3 | 59.1, CH3 | 3.71 s | C-1′, C-2′, C-3 | 59.1 | 3.69 s | C-1′, C-2′, C-3 | ||
| 2′ | 213.2, qC | 213.5 | ||||||
| 3′ | 81.0, CH | 4.71 d (2.8) | C-2′, C-4′, C-5′ | H-4′, H-5′ | 81.1 | 4.70 d (2.8) | C-2′, C-4′, C-5′ | H-4′, H-5′ |
| 4′ | 69.3, CH | 4.84 dq (6.2 and 2.8) | C-2′, C-3′, C-5′ | H-5′, H-3′ | 69.4 | 4.84 dq (6.0 and 2.8) | C-2′, C-3′, C-5′ | H-5′, H-3′ |
| 5′ | 20.7, CH3 | 1.60 d (6.2 Hz) | C-3′, C-4′ | H-4′, H-3′ | 20.7 | 1.59 d (6.0) | C-3′, C-4′ | H-4′, H-3′ |
| 1A | 97.9, CH | 5.67 d (9.6 and 2.0) | C-6 | H-5, H-5A, H-3A, H-2Aeq, H-10 | 98.0 | 5.63 dd (9.6 and 2.0) | C-6 | H-5, H-3A, H-5A, H-2Aeq |
| 2Aax | 37.6, CH2 | 2.25 ddd (12, 12 and 9.6) | C-1A, C-3A | H-4A, H-2Aeq | 36.7 | 2.00 ddd (12.0, 12.0 and 9.6) | C-1A, C-3A, C-4A | H-4A, H-2Aeq |
| 2Aeq | 2.72 ddd (12, 5.0 and 2.0) | H-1A, H-3A, H-2Aax | 2.73 ddd (12.0, 5.0 and 2.0) | H-1A, H-2Aax | ||||
| 3A | 80.0, CH | 4.28 ddd (12, 9.0 and 5.0) | C-1B, C-4A | H-1A, H-1B, H-5A | 74.2 | 4.35 ddd (12, 9.2 and 5.0) | C-2A, 4A | H-1A, H-5A |
| 4A | 75.9, CH | 3.63 t (9.0) | C-3A, C-5A, C-6A | H-2Aax, H3-6A | 75.4 | 3.63 t (9.2) | C-3A, C-5A, C-6A | H-2Aax, H3-6A |
| 5A | 73.8, CH | 3.99 dq (9.0 and 6.0) | C-4A, C-6A | H-1A, H-3A, H3-6A | 73.8 | 4.01 dq (9.2 and 6.0 Hz) | C-1A, C-3A, C-4A, C-6A | H-1A, H-3A, H3-6A |
| 6A | 19.0, CH3 | 1.71 d (6.0) | C-5A, C-4A | H-4A, H-5A | 19.4 | 1.70 d (6.0) | C-4A, C-5A | H-4A, H-5A |
| 1B | 99.4, CH | 5.05 dd (9.6 and 2.0) | C-3A | H-3B, H-3A, H-2Bax, H-2Beq, H-5B | ||||
| 2Bax | 41.2, CH2 | 2.17 ddd (12, 12 and 9.6) | C-1B, C-3B | H-1B, H-4B | ||||
| 2Beq | 2.65 ddd (12, 5.0 and 2.0) | H-1B | ||||||
| 3B | 72.1, CH | 4.14 ddd (12, 9.0 and 5.0) | C-4B | H-1B, H-5B | ||||
| 4B | 78.5, CH | 3.58 t (9.0) | C-5B, C-6B | H-2Bax | ||||
| 5B | 73.7, CH | 3.75 dq (9.0 and 6.0) | C-4B, C-6B | H-1B, H-3B, H3-6B | ||||
| 6B | 18.9, CH3 | 1.64 d (6.0) | C-4B, C-5B | H-5B | ||||
| 1C | 101.6, CH | 5.40 dd (9.6 and 2.0) | C-2 | H-2, H-3C, H-5C, H-2Ceq | 101.7 | 5.40 dd (9.6 and 2.0) | C-2 | H-2, H-5C, H-3C, H-2Ceq |
| 2Cax | 38.5, CH2 | 2.02 ddd (12, 12 and 9.6) | C-3C | H-4C | 38.4 | 2.02 ddd (12, 12 and 9.6) | C-1C, C-3C, C-4C | H-4C |
| 2Ceq | H-1C2.99 ddd (12, 5.0 and 2.0) | 2.99 ddd (12, 5.0 and 2.0) | ||||||
| 3C | 81.1, CH | 4.03 ddd (12, 9.0 and 5.0) | C-1D, C-4C | H-1C, H-1D, H-5C, H-2Ceq | 81.6 | 4.06 ddd (12, 9.0 and 5.0) | C-1D, C-4C | H-1C, H-5C, H-1D |
| 4C | 76.3, CH | 3.48 t (9.0) | C-3C, C-5C | H-2Cax, H3-6C | 76.2 | 3.47 t (9.0) | C-3C, C-5C, C-6C | H-2Cax, H3-6C |
| 5C | 73.6, CH | 3.69 dq (9.0 and 6.0) | C-4C, C-6C | H-3C, H-1C, H3-6C | 73.3 | 3.67 dq (9.0 and 6.0) | C-1C, C-4C, C-6C | H-1C, H-3C, H3-6C |
| 6C | 18.7, CH3 | 1.58 d (6.0) | C-4C, C-5C | H-4C, H-5C | 18.9 | 1.60 d (6.0) | C-4C, C-5C | H-5C |
| 1D | 98.9, CH | 5.46 dd (9.6 and 2.0) | C-3C | H-3C, H-5D | 100.3 | 4.79 dd (9.6 and 2.0) | C-3C | H-3C, H-3D, H-5D |
| 2Dax | 45.2, CH2 | 1.86 dd (13.0 and 9.6) | C-1D, C-3D | H-2Deq | 33.1 | 2.42 ddd (12, 12 and 9.6) | C-1D, C-3D, C-4D | |
| 2Deq | 2.33 dd (13.0 and 2.0) | H-2Dax | 2.18 ddd (12, 5.0 and 2.0) | |||||
| 3D | 71.2, CH | 77.0 | 4.21 ddd (12, 5.0 and 2.5) | C-1E, C-4D | H-1D, H-5D, H-1E | |||
| 3D-CH3 | 27.9, CH3 | 1.50 s | C-2D, C-4D, C-3D | H-4D | ||||
| 4D | 77.4, CH | 3.35 d (9.2) | C-3D, C-5D | 69.9 | 4.10 br d (2.5) | C-3D, C-5D | H-5D, H3-6D | |
| 5D | 72.1, CH | 4.29 dq (9.2 and 6.2) | C-4D, C-6D | H-1D | 72.1 | 3.75 dq (6.2 and 2.5) | C-1D, C-4D, C-6D | H-1D, H-3D, H-4D |
| 6D | 19.0, CH3 | 1.61 d (6.2 Hz) | C-4D, C-5D | H-5D, 3D-CH3 | 17.5 | 1.54 d (6.2) | C-4D, C-5D | H-4D, H-5D |
| 1E | 98.4 | 5.55 dd (9.6 and 2.0) | C-3D | H-2Eax, H-2Eeq, H-5E, H-3D | ||||
| 2Eax | 45.5 | 1.89 dd (13.0 and 9.6) | C-1E, C-3E, C-4E | H-1E, H-4E | ||||
| 2Eeq | 2.32 dd (13.0 and 2.0) | H-1E | ||||||
| 3E | 71.2 | - | - | - | ||||
| 3E-CH3 | 28.2 | 1.50 s | C-2E, C-4E, C-3E | H-4E | ||||
| 4E | 77.7 | 3.38 d (9.2) | C-3E, C-5E | H3-3E, H3-6E, H-2Eax | ||||
| 5E | 71.9 | 4.29 dq (9.2 and 6.0) | C-1E, C-4E, C-6E | H-1E, H3-6E | ||||
| 6E | 19.0 | 1.61 d (6.0) | C-4E, C-5E | H-4E, H-5E | ||||