The diterpene ent-18,19-dihydroxytrachylobane was biotransformed for the first time by Rhizopus stolonifer, and yielded the new ent-11β,18,19-trihydroxytrachylobane derivative besides the new ent-kaur-11-ene diterpenes ent-16α,18,19-trihydroxykaur-11-ene and ent-18,19-dihydroxy-16α-methoxykaur-11-ene. Their structures were determined by spectrometric methods.
ent-trachylobane diterpene; ent-kaur-11-ene diterpenes; biotransformation; Rhizopus stolonifer ; fungus
| H | 1a a 500 MHz, CDCl3; | 2b b 300 MHz, CD3OD; | 3c c 500 MHz, CD3OD. | 4b b 300 MHz, CD3OD; |
|---|---|---|---|---|
| 1 | 1.52 (d, J 11.1 Hz, Hα) | 1.51 (br s, Hα) | 1.79 (d, J 13.4 Hz, Hα) | 1.81 (br s, 2H) |
| 0.78 (td, J 7.5 and 2.4 Hz, Hβ) | 0.78 (d, J 3.5 Hz, Hβ) | 1.03 (td, J 12.9 and 3.3 Hz, Hβ) | ||
| 2 | 1.55 (m, Hα) | 1.42 (br s, J 2.4 Hz, 2H) | 1.62 (m, Hα) | 1.48 (br s, 2H) |
| 1.35 (m, Hβ) | 1.47 (m, Hβ) | |||
| 3 | 2.00 (d, J 11.6 Hz, Hα) | 1.47 (br s, 2H) | 1.74 (d, J 1.6 Hz, Hα) | 1.35 (s, 2H) |
| 0.96 (m, Hβ) | 1.20 (br s, Hβ) | |||
| 5 | 0.94 (m, 1H) | 1.23 (s, 1H) | 1.34 (m, 1H) | 1.35 (s, 1H) |
| 6 | 1.60 (m, 2H) | 1.68 (s, Hα) | 1.60 (m, Hα) | 1.35 (s, Hα) |
| 1.07 (s, Hβ) | 1.34 (m, Hβ) | 1.61 (s, Hβ) | ||
| 7 | 1.35 (m, 2H) | 2.04 (br s, Hα) | 1.69 (d, J 10.3 Hz, Hα) | 1.61 (br s, 2H) |
| 1.99 (br s, Hβ) | 1.59 (d, J 4.1 Hz, Hβ) | |||
| 9 | 1.14 (m, 1H) | 1.29 (m, 1H) | 1.46 (br s, 1H) | 1.48 (br s, 1H) |
| 11 | 1.88 (td, J 13.0 and 3.0 Hz, Hα) | 4.11 (s, 1H) | 5.55 (dd, J 8.2 and 3.6 Hz, 1H) | 5.59 (dd, J 8.5 and 3.7 Hz, 1H) |
| 1.64 (ddd, J 13.6, 6.1 and 1.8 Hz, Hβ) | ||||
| 12 | 0.56 (d, J 7.5 Hz, 1H) | 1.02 (t, J 4.0 Hz, 1H) | 5.92 (t, J 8.2 Hz, 1H) | 5.89 (t, J 8.5 Hz, 1H) |
| 13 | 0.80 (dd, J 7.5 and 2.4 Hz, 1H) | 0.83 (m, 1H) | 2.18 (dd, J 6.2 and 3.2 Hz, 1H) | 2.45 (m, 1H) |
| 14 | 2.02 (m, Hα) | 1.68 (s, Hα) | 1.83 (d, J 10.9 Hz, Hα) | 1.77 (s, 2H) |
| 1.14 (m, Hβ) | 1.07 (s, Hβ) | 1.62 (m, Hβ) | ||
| 15 | 1.36 (d, J 11.2 Hz, Hα) | 1.68 (s, Hα) | 1.47 (br s, 2H) | 1.59 (br s, Hα) |
| 1.23 (d, J 11.2 Hz, Hβ) | 1.07 (s, Hβ) | 1.61 (br s, Hβ) | ||
| 17 | 1.12 (s, 3H) | 1.15 (s, 3H) | 1.27 (s, 3H) | 1.29 (br s, 3H) |
| 18 | 3.88 (d, J 10.5 Hz, Hα) | 3.52 (d, J 11.0 Hz, Hα) | 3.54 (d, J 11.1 Hz, 2H) | 3.56 (d, J 11.3 Hz, Hα) |
| 3.33 (d, J 10.5 Hz, Hβ) | 3.46 (d, J 11.0 Hz, Hβ) | 3.47 (d, J 11.3 Hz, Hβ) | ||
| 19 | 3.91 (d, J 10.5 Hz, Hα) | 3.76 (d, J 11.2 Hz, Hα) | 3.77 (d, J 3.0 Hz, 2H) | 3.54 (d, J 12.1 Hz, Hα) |
| 3.71 (d, J 10.5 Hz, Hβ) | 3.50 (d, J 11.2 Hz, Hβ) | 3.49 (d, J 12.1 Hz, Hβ) | ||
| 20 | 0.90 (s, 3H) | 0.90 (s, 3H) | 0.96 (s, 3H) | 0.95 (s, 3H) |
| OCH3 | - | - | - | 3.13 (s) |
| C | 1a a 125 MHz, CDCl3; | 2b b 75 MHz, CD3OD; | 3c c 125 MHz, CD3OD. | 4b b 75 MHz, CD3OD; |
|---|---|---|---|---|
| 1 | 39.0 | 40.17 | 40.69 | 40.71 |
| 2 | 17.3 | 18.56 | 18.79 | 18.79 |
| 3 | 30.4 | 30.70 | 30.63 | 30.64 |
| 4 | 41.7 | 43.33 | 43.56 | 43.56 |
| 5 | 53.5 | 51.23 | 49.81 | 49.91 |
| 6 | 20.7 | 20.81 | 21.33 | 21.32 |
| 7 | 39.3 | 32.26 | 42.39 | 42.44 |
| 8 | 40.6 | 48.12 | 44.51 | 44.14 |
| 9 | 53.5 | 56.40 | 63.97 | 64.02 |
| 10 | 38.2 | 39.25 | 39.31 | 39.32 |
| 11 | 21.1 | 73.17 | 128.28 | 129.00 |
| 12 | 20.7 | 32.06 | 133.95 | 133.64 |
| 13 | 24.4 | 25.65 | 51.18 | 45.97 |
| 14 | 33.5 | 20.81 | 35.18 | 34.83 |
| 15 | 50.5 | 46.76 | 59.73 | 57.45 |
| 16 | 22.6 | 25.10 | 84.42 | 90.10 |
| 17 | 20.7 | 20.81 | 25.92 | 19.93 |
| 18 | 74.0 | 69.76 | 69.79 | 69.79 |
| 19 | 65.0 | 64.18 | 64.18 | 64.18 |
| 20 | 15.1 | 15.94 | 18.64 | 18.65 |
| OCH3 | - | - | - | 49.82 |
