New Lamellarin Alkaloids from the Australian Ascidian, Didemnum chartaceum

Five novel lamellarin-class alkaloids have been isolated from a Great Barrier Reef ascidian, Didemnum chartaceum. The structures of the 20-sulfated derivatives of lamellarins B, C, and L (1-3); the 8-sulfated derivative of lamellarin G (4), plus a nonsulfated compound, lamellarin Z (5), were identified by interpretation of spectroscopic data. Lamellarin G 8-sulfate (4) is the first example of this class of compounds sulfated at the C-8 position, while lamellarin Z (5) is the first example of a dimethoxylated lamellarin. The known lamellarins A, B, C, E, G, and L (6-11), plus the triacetate derivatives of lamellarins D (12) and N (13), were also isolated. An aberration in the integration of signals in the 1H NMR spectra of the 20-sulfated derivatives of lamellarins B, C, and L (1-3) led to NMR relaxation studies. T1 values were calculated for all protons in the sulfated lamellarins (1-4) and their corresponding nonsulfated derivatives (7, 8, 10, 11). Interestingly, the protons ortho to the sulfate group in compounds (1-4) had T1 values up to five times larger than the corresponding protons in their nonsulfated derivatives (7, 8, 10, 11).