Seven new metabolites, 3‐hydroxy‐1‐(2,6‐dihydroxyphenyl)butan‐1‐one (1), 1‐(2‐hydroxy‐6‐methoxyphenyl)butan‐1‐one (3), 2,3‐dihydro‐5‐methoxy‐2‐methylchromen‐4‐one (6), the dimeric naphthalenes nodulisporin A (9) and B (10), and the first naturally occurring dimeric indanone, nodulisporin C (12), as well as (4E,6E)‐2,4,6‐trimethylocta‐4,6‐dien‐3‐one (13) were isolated together with ten known compounds (2, 4, 5, 7, 8, 11, 14–17) from the culture extract of the endophytic fungus Nodulisporium sp. from Juniperus cedre from Gomera Island. The structure of dictafolin‐A, previously erroneously assigned as structure 6, is not identical with 2,3‐dihydro‐5‐methoxy‐2‐methylchromen‐4‐one, isolated in this investigation. The structures of new compounds were determined by spectroscopic methods (mainly extensive 1D and 2D NMR experiments and mass spectral measurements) and X‐ray single crystal analysis. All but one of the thirteen tested compounds exhibit herbicidal, antifungal and/or antibacterial activities. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Two new curvularin-type macrolides, curvulone A (1) and B (2), and two known ones (3a, 4) of the rare 15R series have been isolated from the fungus Curvularia sp., which has been isolated from the marine alga Gracilaria folifera. Their structures were determined by extensive 2D NMR experiments and supported by the single-crystal X-ray analysis of 1. The structural elucidation of 1, which has a benzo[b]furanone moiety as part of a 12-membered macrolactone, has led to a revision of the structure of the previously reported (11S,15S)-11β-hydroxy-12-oxocurvularin. The absolute configuration of curvulone A was established independently by the solid-state TD-DFT ECD method and by measuring the anomalous dispersion effect. The absolute configuration of curvulone B was determined by TD-DFT ECD calculations on the computed solution conformers. Two different solid-state conformers of 4 were identified by X-ray analysis of the single crystals obtained from different solvents; TD-DFT ECD calculations were performed to reproduce the experimental ECD spectra. All four metabolites were biologically active against fungal, bacterial and algal test organisms

The quantitative methods developed herein should facilitate investigation of the biosynthesis of tolyporphins (and other tetrapyrroles) as well as examination of other strains for production of tolyporphins. Copyright © 2017 John Wiley & Sons, Ltd.

The lipid extract of an Indonesian Lendenfeldia sp. sponge inhibited hypoxia-induced hypoxiainducible factor-1 (HIF-1) activation in T47D breast tumor cells. Chromatographic separation yielded the new substituted naphthalene dimer 1, the new furanolipid 2, and three known Marine natural products continue to be an invaluable source of new molecular-targeted antitumor agents. 1 An ongoing research program was initiated to discover potent and selective small molecule inhibitors of hypoxia-mediated tumor cell adaptation, survival and metastatic spread. 2 The primary molecular target for this drug discovery effort is the transcription factor hypoxia-inducible factor-1 (HIF-1), a heterodimer composed of the oxygen-regulated HIF-1α and the constitutively expressed HIF-1β subunits. 3 Numerous studies strongly support HIF-1 as a valid molecular target for drug discovery that targets tumor hypoxia. 4 Terrestrial and marine organisms have been shown to produce natural products that inhibit HIF-1. 5 The NCI Open Repository of marine invertebrates and algae lipid extracts was examined for HIF-1 inhibitory activity using a T47D human breast carcinoma cell-based reporter assay. 2 The crude extract of the sponge Lendenfeldia sp. (Spongiidae) inhibited hypoxia-induced HIF-1 activation (99% inhibition at 5 μg mL -1 ).The extract (4 g) was purified by silica gel column chromatography and preparative TLC to yield two structurally unrelated new compounds (1 and 2) and three known homoscalarane sesterterpenes (3 -5). The 1 H-13 C HMBC spectrum of 1 exhibited long-range correlations from C-2 to H-3, H-4, C-2-OCH 3 ; from C-1 to H-3, H-8; from C-5 to H-4, H-7; from C-9 to H-4, H-7, H-8; and from C-10 to H-3, H-4, and H-8. Therefore, the substitution pattern for each of the symmetrically substituted naphthalene ring systems was readily established. Compound 1 was optically active ([α] 25 D +10.4). The CD spectrum displayed a positive split Cotton effect indicating that 1 exhibits a right-handed helicity, signifying "S"-configuration. Thus, the structure of 1 was determined to be (S)-2,2′-dimethoxy-1,1′-binaphthyl-5,5′,6,6′-tetraol.Compound 2 was isolated as colorless oil. The HRESIMS indicated that the molecular formula of 2 is C 21 H 34 O. The 1 H NMR spectrum (Table 2) exhibited resonances typical of a β-substituted furan [δ 7.33 (1H, brs), 7.20 (1H, brs), 6.27 (1H, brs)]. The 13 C NMR spectrum (Table 2) contained resonances for 21 carbons, and the 13 C DEPT spectrum indicated the presence of three methyl, ten methylene, five methane, and three quaternary carbon atoms. Analysis of the 1 H-1 H COSY and 1 H-13 C HMQC spectra suggested that the structure of 2 contained four spin systems: -CH(1)-CH(2)-, -CH 2 (5)-CH 2 (6)-CH (7) H spin systems were connected through the observation of longrange 1 H-13 C correlations in the HMBC spectrum from C-3 to H-1, H-2, H-4, H-5, H-6; from C-8 to H-6, H-7, H-9, H-10, H-20; and from C-12 to H-10, H-11, H-13, H-14, H-21. Therefore, the structure was deduced to be that of a new furanolipid.The ...

Tolyporphins are tetrapyrrole macrocycles produced by a cyanobacterium-containing culture known as HT-58-2. Tolyporphins A-J are free base dioxobacteriochlorins, whereas tolyporphin K is an oxochlorin. Here, the photophysical characterization is reported of tolyporphin A and two synthetic analogues, an oxobacteriochlorin and a dioxobacteriochlorin. The characterization (in toluene, diethyl ether, ethyl acetate, dichloromethane, 1-pentanol, 2-butanone, ethanol, methanol, N,N-dimethylformamide and dimethylsulfoxide) includes static absorption and fluorescence spectra, fluorescence quantum yields and time-resolved data. The data afford the lifetime of the lowest singlet excited state and the yields of the nonradiative decay pathways (intersystem crossing and internal conversion). The three macrocycles exhibit only modest variation in spectroscopic and excited-state photophysical parameters across the solvents. The long-wavelength (Q ) absorption band of tolyporphin A appears at ~680 nm and is remarkably narrow (full-width-at-half-maximum ~7 nm). The position of the long-wavelength (Q ) absorption band of tolyporphin A (~680 nm) more closely resembles that of chlorophyll a (662 nm) than bacteriochlorophyll a (772 nm). The absorption spectra of tolyporphins B-I, K (which were available in minute quantities) are also reported in methanol; the spectra of B-I closely resemble that of tolyporphin A. Taken together, tolyporphin A generally exhibits spectral and photophysical features resembling those of chlorophyll a.