Table 1.
1H-NMR and 13C-NMR chemical shifts (Figure 4—source data 1) of novel oxygenated 13R-(+)-manoyl oxide-derived diterpenoids formed following transient expression of CYP encoding genes from C. forskohlii.
| 19-hydroxy- 13R-manoyl oxide (3c)* |
2-hydroxy- 13R-manoyl oxide (3b)* |
1,11-dihydroxy- 13R-manoyl oxide (5d)* |
||||
|---|---|---|---|---|---|---|
| Pos. | 1H (nH; m; J(Hz)) | 13C | 1H (nH; m; J(Hz)) | 13C | 1H (nH; m; J(Hz)) | 13C |
| 1 | 0.89 (1H;m) 1.63 (1H; m) |
39.1 | 1.10 (1H; t(br); 11.9, 11.9) 1.77 (1H; m) |
51.3 | 3.49 (1H; dd;11.1, 4.5) |
79.0 |
| 2 | 1.44 (1H; m) 1.56 (1H; m) |
18.1 | 3.92 (1H; m) | 65.3 | 1.75 (1H; td; 13.5, 11.1, 3.9) 1.60 (1H; m) |
29.0 |
| 3 | 0.95 (1H; m) 1.78 (1H; m) |
35.8 | 0.76 (1H; t(br); 11.9, 11.9) 1.99 (1H; d(br); 11.9) |
48.2 | 1.47 (1H; dd; 13.6, 3.9) 1.39 (1H; td; 13.5, 3.6) |
39.6 |
| 4 | 38.5 | 34.9 | 33.4 | |||
| 5 | 1.10 (1H; dd; 2.3, 12.6) | 56.9 | 0.95 (1H; dd; 2.2, 12.4) | 55.9 | 0.84 (1H; dd; 11.3, 2.0) | 55.6 |
| 6 | 1.36 (1H; dd; 3.6, 12.6) | 20.1 | 1.68 (1H; m) | 19.7 | 1.47 (1H; m) | 20.2 |
| 1.75 (1H; m) | 1.27 (1H; m) | 1.64 (1H; m) | ||||
| 7 | 1.42 (1H; m) 1.83 (1H; dt; 3.3, 12.2) |
43.6 | 1.45 (1H; dd(br); 3.6, 12.5) 1.85 (1H; dt(br); 2.9, 12.5) |
43.2 | 1.48 (1H; m) 1.85 (1H; m) |
44.0 |
| 8 | 75.1 | 75.1 | 75.3 | |||
| 9 | 1.35 (1H; dd; 4.3, 12.0) | 55.7 | 1.40 (1H; dd; 4.2, 11.9) | 55.4 | 1.54 (1H; d; 5.8) | 55.8 |
| 10 | 37.3 | 38.7 | 43.8 | |||
| 11 | 1.48 (1H; m) 1.58 (1H; m) |
15.4 | 1.53 (1H; m) 1.61 (1H; m) |
15.6 | 4.38 (1H; br q; ≈8.6) |
65.6 |
| 12 | 1.78 (1H; m) 1.64 (1H; m) |
35.7 | 1.78 (1H; m) 1.66 (1H; m) |
35.5 | 2.02 (1H; dd; 14.3, 8.7) 2.27 (1H; dd; 14.3, 8.7) |
35.8 |
| 13 | 73.4 | 73.4 | 72.8 | |||
| 14 | 5.87 (1H; dd; 10.8, 17.4) | 147.7 | 5.87 (1H; dd; 10.8, 17.4) | 147.7 | 5.90 (1H; dd; 17.4, 10.8) | 147.1 |
| 15 | 4.92 (1H; dd; 1.5, 10.8) 5.14 (1H; dd; 1.5, 17.4) |
110.2 | 4.92 (1H; d; 10.8) 5.14 (1H; d; 17.4) |
110.3 | 4.94 (1H; dd; 10.7, 1.5) 5.17 (1H; dd; 17.4, 1.5) |
111.2 |
| 16 | 1.27 (3H; s) | 28.5 | 1.27 (3H; s) | 28.7 | 1.27 (3H; s) | 32.1 |
| 17 | 1.28 (3H; s) | 25.3 | 1.29 (3H; s) | 25.7 | 1.49 (3H; s) | 27.8 |
| 18 | 0.97 (3H; s) | 26.8 | 0.93 (3H; s) | 33.5 | 0.78 (3H; s) | 13.5 |
| 19 | 3.70 (1H; d; 10.9) 3.46 (1H; d; 10.9) |
65.4 | 0.85 (3H; s) | 22.2 | 0.85 (3H; s) | 32.8 |
| 20 | 0.78 (3H; s) | 15.7 | 0.84 (3H; s) | 16.5 | 0.79 (3H; s) | 21.1 |
* 1H and 13C NMR data acquired at 600 and 150 MHz, respectively, in methanol-d4, at 300 K. s = singlet, d = doublet, t = triplet, m = multiplet, br = broad.