Patellazole C: a novel cytotoxic macrolide from Lissoclinum patella

Journal of the American Chemical Society
1988.0

Abstract

The didemnid tunicate Lissoclinum patella collected in Palau produces unique cytotoxic cyclic peptides containing thiazole amino acids, while we now report that L. patella from the Fiji Islands produces a new family of novel thiazole-containing polyketide metabolites, the patellazoles A-C (1-3). The patellazoles were potent cytotoxins in the NCI human cell line protocol with mean IC50 values of 10-3-104 pg/mL and showed antifungal activity against Candida albicans. From 220 g of freeze-dried and pulverized L. patella, a MeOH extract was partitioned, and the active component was concentrated in the CCl4 fraction. Gravity column chromatography on silica gel 62 followed by successive reverse-phase and silica gel HPLC afforded 97 mg of patellazole A (1), 143 mg of patellazole B (2), and 313 mg of patellazole C (3). We report the structure determination of patellazole C (3): its molecular formula C49H77NO13S was assigned by FABMS mass measurement of the MH+ ion (920.5179, required 920.5197). Spectroscopic data (UV, IR, NMR including DEPT, double quantum filtered phase sensitive COSY, 1H-13C chemical shift correlation, INAPT, COLOC, and 2D INADEQUATE experiments) and chemical degradation (ozonolysis to thiazole 4) were used. DEPT experiments established 71 carbon-bound protons (13 methyls, 6 methylenes, 20 methines); D2O exchange experiments indicated six active protons. NMR data indicated an epoxy thiazole moiety, confirmed by ozonolysis. Combination of NMR experiments connected partial structures to establish a 24-membered macrolide. The patellazoles represent a new class of macrolides incorporating an unusual thiazole moiety.

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