Table 3.
13C and 1H NMR chemical shifts and HMBC and ROESY correlations of carbohydrate moiety of chitonoidoside K (3).
| Atom | δC Mult. a, b, c | δH Mult. (J in Hz) d | HMBC | ROESY |
|---|---|---|---|---|
| Xyl1 (1→C-3) | ||||
| 1 | 104.6 CH | 4.57 d (7.3) | C: 3 | H-3; H-3, 5 Xyl1 |
| 2 | 82.9 CH | 3.69 t (8.7) | C: 1 Qui2; 1, 3 Xyl1 | H-1 Qui2 |
| 3 | 75.1 CH | 3.92 m | C: 4 Xyl1 | H-1, 5 Xyl1 |
| 4 | 80.3 CH | 3.93 m | H-1 Glc5 | |
| 5 | 63.4 CH2 | 4.27 dd (4.7; 12.1) | C: 3 Xyl1 | |
| 3.52 m | H-1 Xyl1 | |||
| Qui2 (1→2Xyl1) | ||||
| 1 | 104.6 CH | 4.72 d (8.6) | C: 2 Xyl1 | H-2 Xyl1; H-3, 5 Qui2 |
| 2 | 75.5 CH | 3.84 t (8.6) | C: 1, 3 Qui2 | H-4 Qui2 |
| 3 | 74.4 CH | 3.95 t (8.6) | C: 2, 4 Qui2 | |
| 4 | 86.1 CH | 3.25 t (8.6) | C: 1 Glc3; 3, 5 Qui2 | H-1 Glc3; H-2 Qui2 |
| 5 | 71.6 CH | 3.53 dd (5.7; 8.6) | H-1, 3 Qui2 | |
| 6 | 17.5 CH3 | 1.48 d (5.7) | C: 4, 5 Qui2 | H-4, 5 Qui2 |
| Glc3 (1→4Qui2) | ||||
| 1 | 103.9 CH | 4.64 d (7.9) | C: 4 Qui2 | H-4 Qui2; H-3, 5 Glc3 |
| 2 | 74.5 CH | 3.73 t (9.1) | C: 1, 3 Glc3 | |
| 3 | 86.3 CH | 4.10 t (9.1) | C: 1 MeGlc4; 4 Glc3 | H-1 MeGlc4; H-1 Glc3 |
| 4 | 69.2 CH | 3.64 t (9.1) | C: 3, 5, 6 Glc3 | |
| 5 | 74.3 CH | 4.04 t (9.1) | H-1 Glc3 | |
| 6 | 67.5 CH2 | 4.87 dd (4.2; 11.0) | ||
| 4.49 dd (6.9; 11.0) | C: 5 Glc3 | |||
| MeGlc4 (1→3Glc3) | ||||
| 1 | 104.6 CH | 5.11 d (8.0) | C: 3 Glc3 | H-3 Glc3; H-3, 5 MeGlc4 |
| 2 | 74.2 CH | 3.74 t (8.0) | C: 1, 3 MeGlc4 | |
| 3 | 86.4 CH | 3.58 t (8.0) | C: 4 MeGlc4, OMe | H-1, 5 MeGlc4; OMe |
| 4 | 69.8 CH | 3.96 t (8.0) | C: 3, 5 MeGlc4 | H-6 MeGlc4 |
| 5 | 75.5 CH | 3.96 m | C: 6 MeGlc4 | H-1, 3 MeGlc4 |
| 6 | 67.0 CH2 | 4.88 d (11.6) | ||
| 4.69 dd (3.5; 11.6) | C: 5 MeGlc4 | |||
| OMe | 60.5 CH3 | 3.70 s | C: 3 MeGlc4 | |
| Glc5 (1→4Xyl1) | ||||
| 1 | 103.2 CH | 4.80 d (8.4) | C: 4 Xyl1 | H-4 Xyl1; H-3, 5 Glc5 |
| 2 | 73.2 CH | 3.77 t (8.4) | C: 1 Glc5 | |
| 3 | 86.2 CH | 4.08 t (9.1) | C: 1 MeGlc6; 2 Glc5 | H-1 MeGlc6; H-1 Glc5 |
| 4 | 69.4 CH | 3.67 t (9.1) | ||
| 5 | 74.4 CH | 4.07 m | ||
| 6 | 67.7 CH2 | 4.90 d (11.0) | ||
| 4.43 dd (7.8; 11.0) | C: 5 Glc5 | |||
| MeGlc6 (1→3Glc5) | ||||
| 1 | 104.5 CH | 5.07 d (7.8) | C: 3 Glc5 | H-3 Glc5; H-3, 5 MeGlc6 |
| 2 | 74.3 CH | 3.72 t (7.8) | C: 1, 3 MeGlc6 | |
| 3 | 86.4 CH | 3.57 t (7.8) | C: 4 MeGlc6, OMe | H-1, 5 MeGlc6 |
| 4 | 69.8 CH | 3.95 m | C: 3, 5 MeGlc6 | H-6 MeGlc6 |
| 5 | 75.5 CH | 3.95 m | H-1, 3 MeGlc6 | |
| 6 | 67.0 CH2 | 4.87 d (11.0) | C: 4, 5 MeGlc6 | |
| 4.69 dd (2.6; 11.0) | ||||
| OMe | 60.5 CH3 | 3.71 s | C: 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 Figures S17–S23.