Table 3.
400 MHz 1H NMR Data of 3, 8 and 9 in DMSO-d6 and 12–14 in CDCl3 (δH, J in Hz) a.
| Position | 3 b | 8 | 9 | 12 | 13 | 14 |
|---|---|---|---|---|---|---|
| 1 | 5.55 dd (8.1, 6.4) | 5.56 dd (8.3, 6.3) | 5.55 dd (8.1, 6.5) | 5.55 dd (8.2, 6.2) | 5.54 m | 5.56 dd (8.4, 6.3) |
| 2α | 2.07 m | 2.07 m | 2.07 m | 2.23 m | 2.22 m | 2.24 ddt (13.4, 8.4, 2.2) |
| β | 2.34 ddd (13.3, 11.4, 6.4) | 2.34 m | 2.34 m | 2.47 ddd (13.4, 11.3, 6.2) | 2.46 ddd (13.1, 11.4, 6.0) | 2.48 ddd (13.4, 11.3, 6.3) |
| 3 | 3.11 m | 3.12 m | 3.12 m | 3.47 m | 3.46 m | 3.50 m |
| 4α | 2.63 br d (13.0) | 2.63 br d (13.2) | 2.63 br d (13.1) | 2.87 br d (12.8) | 2.87 br d (12.8) | 2.89 br d (13.0) |
| β | 1.52 m | 1.53 m | 1.52 m | 1.68 m | 1.67 m | 1.66 m |
| 5 | 2.69 m | 2.68 m | 2.68 m | 2.72 m | 2.71 m | 2.74 m |
| 7 | 5.43 s | 5.43 s | 5.43 s | 5.55 br s | 5.54 br s | 5.58 br s |
| 9 | 2.84 dd (11.2, 6.0) | 2.85 dd (11.5, 5.5) | 2.85 dd (11.5, 5.4) | 2.74 dd (12.5, 5.8) | 2.73 dd (12.6, 5.8) | 2.76 dd (12.0, 5.8) |
| 11α | 1.50 m | 1.54 m | 1.54 m | 1.56 m | 1.55 m | 1.59 m |
| β | 1.77 m | 1.79 m | 1.78 m | 1.65 m | 1.64 m | 1.86 m |
| 12α | 1.41 td (12.4, 4.0) | 1.49 m | 1.49 m | 1.43 td (13.0, 4.8) | 1.42 m | 1.47 td (13.1, 4.4) |
| β | 1.68 m | 1.75 m | 1.75 m | 2.18 m | 2.17 m | 2.16 m |
| 14 | 2.29 br t (7.9) | 2.26 br t (9.2) | 2.25 br t (9.2) | 2.06 ddd (12.0, 6.4, 1.5) | 2.05 ddd (12.4, 6.6, 1.4) | 2.08 ddd (12.0, 6.1, 1.6) |
| 15α | 1.62 m | 1.57 m | 1.57 m | 1.46 m | 1.46 m | 1.62 m |
| β | 1.62 m | 1.53 m | 1.52 m | 1.58 m | 1.57 m | 1.54 m |
| 16α | 1.71 m | 1.84 m | 1.83 m | 1.74 m | 1.71 m | 1.91 m |
| β | 1.90 m | 1.70 m | 1.70 m | 1.78 m | 1.77 m | 1.67 m |
| 17 | 2.84 m (covered by H-9 signals) | 2.33 m | 2.33 m | 1.80 m | 1.79 m | 1.68 m |
| 18α | 2.48 br s | 2.48 br s | 2.48 br s | 2.54 br s | 2.53 m | 2.54 d (13.6) |
| β | 2.48 br s | 2.48 br s | 2.48 br s | 2.55 m | 2.54 m | 2.59 dd (13.6, 6.0) |
| 19 | 0.65 s/0.67 s | 0.55 s/0.53 s | 0.54 s/0.53 s | 0.73 s | 0.71 s | 0.86 s |
| 21 | 1.77 s | 1.71 s | 1.68 s | 1.28 s | 1.27 s | 1.25 s |
| 22 | 5.17 dd (10.2, 1.0)/5.14 dd (10.2, 1.0) | 5.02 d (9.4) | 5.12 d (8.9) | 5.66 d (16.0) | 5.67 d (16.0) | 3.90 dd (8.3, 0.6) |
| 23 | 3.84 dd (10.0, 4.0)/3.74 dd (10.0, 5.9) | 3.71 dd (9.4, 6.7) | 3.77 dd (8.9, 4.0)/3.79 dd (8.9, 3.8) | 5.55 dd (16.0, 6.0) | 5.54 dd (16.0, 6.1) | 5.41 ddq (15.3, 8.2, 1.6) |
| 24 | 3.56 m/3.50 m | 3.53 m | 3.60 m | 4.34 m | 4.33 m | 5.77 dqd (15.3, 6.5, 0.6) |
| 25 | 1.03 d (6.3)/1.01 d (6.3) | 0.95 d (6.4)/0.94 d (6.3) | 0.99 d (6.3)/0.97d (6.1) | 1.28 d (6.3) | 1.27 d (6.3) | 1.73 dd (6.5, 1.6) |
| 3-OH | 4.63 d (4.3) | 4.62 d (4.2) | 4.63 d (3.8) | Not detected | Not detected | Not detected |
| 20-OH | - | - | - | - | - | Not detected |
| 24-OH | 4.47 d (4.9) /4.44 d (4.7) | 4.45 d (3.9)/4.44 d (3.8) | 4.44 d (3.6) | Not detected | Not detected | Not detected |
| 20-OCH3 | - | - | - | 3.11 s | 3.12 d (0.7) | - |
| 23-OCH3 | 3.11 s | 3.147 s/3.152 s | 3.15 s/3.16 s | - | - | - |
a Chemical shifts were recorded in δH values using the solvent signals (DMSO-d6: δH 2.50 for 3, 8 and 9; CDCl3: δH 7.26 for 12–14) as references; b The 23-O-methylantineocyclocitrinol (3) was obtained as a mixture of the 23-O-methyl derivatives of 1 (24R) and 2 (24S) in an approximate 4:1 ratio of the 24R and 24S forms. Signals of the H-19, H-22 to H-25 and HO-24 protons appeared as a pair of separated signals in the 1H NMR spectrum and their data are given as the former/latter signals for the 24R and 24S forms, respectively. The signal assignments were based on the results of DEPT, 1H-1H COSY, HMQC, HMBC, NOESY, and 1D difference NOE experiments.