Table 1.
13C and 1H NMR chemical shifts and HMBC and ROESY correlations of carbohydrate moiety of chitonoidoside I (1).
| Atom | δC Mult. a, b, c | δH Mult. (J in Hz) d | HMBC | ROESY |
|---|---|---|---|---|
| Xyl1 (1→C-3) | ||||
| 1 | 104.7 CH | 4.66 d (6.3) | C: 3 | H-3; H-3, 5 Xyl1 |
| 2 | 82.1 CH | 3.93 t (8.1) | C: 1 Qui2; 1 Xyl1 | H-1 Qui2 |
| 3 | 75.1 CH | 4.13 t (8.1) | C: 4 Xyl1 | H-1, 5 Xyl1 |
| 4 | 78.3 CH | 4.13 m | H-1 Glc5 | |
| 5 | 63.5 CH2 | 4.37 brd (11.3) | ||
| 3.64 m | H-1, 3 Xyl1 | |||
| Qui2 (1→2Xyl1) | ||||
| 1 | 104.5 CH | 5.02 d (7.3) | C: 2 Xyl1 | H-2 Xyl1; H-3, 5 Qui2 |
| 2 | 75.7 CH | 3.88 t (8.9) | C: 1, 3 Qui2 | H-4 Qui2 |
| т3 | 74.7 CH | 4.00 t (8.9) | C: 2, 4 Qui2 | H-1, 5 Qui2 |
| 4 | 85.6 CH | 3.48 t (8.9) | C: 1 Xyl3; 3, 5 Qui2 | H-1 Xyl3; H-2 Qui2 |
| 5 | 71.4 CH | 3.68 dd (6.2; 8.9) | H-1, 3 Qui2 | |
| 6 | 17.7 CH3 | 1.60 d (6.2) | C: 4, 5 Qui2 | H-4, 5 Qui2 |
| Xyl3 (1→4Qui2) | ||||
| 1 | 104.3 CH | 4.75 d (7.6) | C: 4 Qui2 | H-4 Qui2; H-3, 5 Xyl3 |
| 2 | 73.3 CH | 3.87 t (8.7) | C: 1, 3 Xyl3 | |
| 3 | 86.5 CH | 4.10 t (8.7) | C: 1 Glc4; 2 Xyl3 | H-1 Glc4; H-1, 5 Xyl3 |
| 4 | 68.7 CH | 3.93 m | ||
| 5 | 65.8 CH2 | 4.13 m | C: 4 Xyl3 | |
| 3.60 m | C: 1 Xyl3 | H-1 Xyl3 | ||
| Glc4 (1→3Xyl3) | ||||
| 1 | 104.4 CH | 5.20 d (7.7) | C: 3 Xyl3 | H-3 Xyl3; H-3, 5 Glc4 |
| 2 | 74.9 CH | 3.93 t (8.6) | C: 1, 3 Glc4 | |
| 3 | 77.2 CH | 4.10 m | C: 4 Glc4 | H-1 Glc4 |
| 4 | 71.1 CH | 3.90 m | C: 5 Glc4 | H-6 Glc4 |
| 5 | 77.7 CH | 3.91 m | H-1 Glc4 | |
| 6 | 62.0 CH2 | 4.39 d (11.2) | ||
| 4.04 dd (5.4; 11.2) | C: 5 Glc4 | |||
| Glc5 (1→4Xyl1) | ||||
| 1 | 102.4 CH | 4.88 d (8.2) | C: 4 Xyl1 | H-4 Xyl1; H-3, 5 Glc5 |
| 2 | 73.6 CH | 3.82 t (8.8) | C: 1, 3 Glc5 | |
| 3 | 85.9 CH | 4.16 t (8.8) | C: 1 MeGlc6 | H-1 MeGlc6; H-1, 5 Glc5 |
| 4 | 69.0 CH | 3.85 t (8.8) | ||
| 5 | 75.5 CH | 4.05 t (8.8) | H-1 Glc5 | |
| 6 | 67.3 CH2 | 4.92 d (11.3) | ||
| 4.64 dd (6.2; 11.3) | ||||
| MeGlc6 (1→3Glc5) | ||||
| 1 | 104.4 CH | 5.17 d (7.6) | C: 3 Glc5 | H-3 Glc5; H-3, 5 MeGlc6 |
| 2 | 74.0 CH | 3.85 t (8.9) | C: 1 MeGlc6 | |
| 3 | 85.2 CH | 3.70 t (8.9) | C: 4 MeGlc6, OMe | H-1 MeGlc6 |
| 4 | 76.1 CH | 4.88 t (8.9) | C: 5 MeGlc6 | H-2 MeGlc6 |
| 5 | 76.3 CH | 3.84 m | H-1 MeGlc6 | |
| 6 | 61.6 CH2 | 4.48 d (11.4) | ||
| 4.32 dd (5.1; 11.4) | ||||
| OMe | 60.7 CH3 | 3.92 s | C: 3 MeGlc6 | H-3 MeGlc6 |
a Recorded at 125.67 MHz in C5D5N/D2O (4/1). b Bold = interglycosidic positions. c Italic = sulfate position. d Recorded at 500.12 MHz in C5D5N/D2O (4/1). Multiplicity by 1D TOCSY. The original spectra of 1 are provided as Figures S1–S7.