Talarofuranone, a New Talaroconvolutin Analog from the Endophytic Fungus Talaromyces purpurogenus from Pouteria campechiana Seeds.

An endophytic fungus Talaronyces pinpurogenus was isolated from the seeds of the popular edible fruit Pouteria campechiana. The fungus was fermented in potato dextrose agar and the fungal media were extracted with EtOAc. Chromatographic separation of the EtOAc extracts over silica gel, Sephadex LH-20 and preparative thin layer chromatography furnished a furanone analogue of talaroconvolutin A, named talarofuranone (1), along with talaroconvolutin A (2), 4-hydroxyactophenone, tyrosol and ergosterol. The structure of 1 was determined by comparing the NMR data with that of 2 and by HRFABMS.

A 3-Vinyl Cephem Derivative, a Useful Intermediate in the Synthesis of Cepham Antibiotics, from Aspergillus awamori Associated with Banana Fruit.

Aspergillus awamori was isolated from a diseased banana fruit, Musa acuminata cv. Ambul. The fungus was fermented in potato dextrose broth and on potato dextrose agar media and the fungal media were extracted with EtOAc. Chromatographic separation of the EtOAc extracts furnished 4-methoxybenzyl 7-phenylacetamido-3-vinyl-3-cephem-4-carboxylate (1), along with three naphtho-γ-pyrones, flavasperone (2), foncesinone A (3) and aurasperone A (4), and three alkaloids, aspernigrin A (5), pestalamide C (6) and nigragillin (7). Compound 1, a known key intermediate in the chemical synthesis of cepham antibiotics, was isolated from a natural source for the first time. Compound 1 is the first 3-vinyl cephem derivative of microbial origin.

Cytotoxic constituents of Abutilon indicum leaves against U87MG human glioblastoma cells.

The study was aimed to identify cytotoxic leads from Abutilon indicum leaves for treating glioblastoma. The petroleum ether extract, methanol extract (AIM), chloroform and ethyl acetate sub-fractions (AIM-C and AIM-E, respectively) prepared from AIM were tested for cytotoxicity on U87MG human glioblastoma cells using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. These extracts exhibited considerable activity (IC50 values of 42.6-64.5 µg/mL). The most active AIM-C fraction was repeatedly chromatographed to yield four known compounds, methyl trans-p-coumarate (1), methyl caffeate (2), syringic acid (3) and pinellic acid (4). Cell viability assay of 1-4 against U87MG cells indicated 2 as most active (IC50 value of 8.2 µg/mL), whereas the other three compounds were much less active. Interestingly, compounds 1-4 were non-toxic towards normal human cells (HEK-293). The content of 2 in AIM-C was estimated as 3% by HPLC. Hence, presence of some more active substances besides methyl caffeate (2) in AIM-C is anticipated.

Stereochemical assignment of C-24 and C-25 of amarasterone A, a putative biosynthetic intermediate of cyasterone.

A C29 phytoecdysteroid named amarasterone A (1) has been isolated from Cyathula capitata (Amaranthaceae), Leuzea carthamoides (Asteraceae), and Microsorum scolopendria (Polypodiaceae). We recently isolated amarasterone A from C. officinalis. Amarasterone A has been postulated as a biosynthetic intermediate of cyasterone in Cyathula sp. The stereochemistry at the C-24 and C-25 positions of these amarasterone A samples was investigated by comparing the NMR spectroscopic data with those of stereodefined model compounds, (24R,25S)-, (24R,25R)-, (24S,25S)-, and (24S,25R)-isomers of (20R,22R)-3ß-methoxystigmast-5-ene-20,22,26-triol (2a-d), which were synthesized in the present study. Amarasterone A isolated from Cyathula officinalis was determined to be the (24R,25S)-isomer (1a), while amarasterone A from L. carthamoides was found to be the (24R,25R)-isomer (1b). Amarasterone A from M. scolopendria was found to be a mixture of 1a and 1b. The biosynthesis of cyasterone in Cyathula sp. is discussed on the basis of the identical C-24 configuration of sitosterol and amarasterone A.

Establishment of benzodioxazine core structure for sarcodonin class of natural products by X-ray analysis.

Sarcodonin ε (2), isolated from Sarcodon scabrosus, was treated with trimethylsilyldiazomethane to yield a crystalline methylated derivative 6. The structure of 6 was determined by X-ray analysis, which confirmed the presence of an unprecedented N(1b)-OMe group, the configuration at N(1b) and the 1,3,4-substituted phenyl ring structure of 2. More importantly, the structures of 6 and 2 have answered the intriguing problem of solving the core structure of the sarcodonin class of natural products, establishing that sarcodonins have a benzodioxazine core structure, rather than the recently proposed benzodioxane aminal core structure.