Online Analysis of Xestodecalactones A−C, Novel Bioactive Metabolites from the Fungus <i>Penicillium cf.</i> <i>m</i><i>ontanense</i> and Their Subsequent Isolation from the Sponge <i>Xestospongia </i><i>e</i><i>xigua</i>

Abstract

Fungal isolates of Penicillium cf. montanense were obtained from the marine sponge Xestospongia exiguacollected from the Bali Sea, Indonesia. Culture filtrates of the fungi yielded three novel decalactone metabolites, xestodecalactones A, B, and C (1, 2a, and 2b), consisting of 10-membered macrolides with a fused 1,3-dihydroxybenzene ring. Online HPLC-NMR, ESI-MS/MS, and -CD spectra were acquired, and the structures of the new compounds were established and confirmed on the basis of offline NMR spectroscopic ((1)H, (13)C, COSY, ROESY, (1)H-detected direct and long-range (13)C-(1)H correlations) and mass spectrometric (EIMS) data. Quantum chemical calculations of the CD spectra proved to be difficult because of the conformational flexibility of the xestodecalactones. These compounds, of which 2a and 2b, due to the additional stereocenter at C-9, are diastereomeric compounds, are structurally related to a number of biologically active metabolites found in terrestrial fungal strains. Compound 2a was found to be active against the yeast Candida albicans.