Hypocriols A–F, Heterodimeric Botryane Ethers from Hypocrea sp., an Insect-Associated Fungus

Abstract

The new heterodimeric botryane ethers hypocriols A-F (1-6) and the known compounds 4β-acetoxy-9β,10β,15α-trihydroxyprobotrydial (7), dihydrobotrydial (8), 10-oxodehydrodihydrobotrydial (9), and dehydrobotrydienol (10) were isolated from the solid cultures of an insect-associated fungus Hypocrea sp. The structures of 1-6 were elucidated primarily by NMR experiments. The absolute configuration of 1 was assigned using the modified Mosher method and electronic circular dichroism (ECD) calculations, whereas those for 3-5, and 2 and 6 were deduced via ECD calculations and circular dichroism data, respectively. Compounds 1-6 appear to be the first heterodimeric botryane ethers and showed antiproliferative effects against a small panel of four human tumor cell lines.

Varicuothiols A and B, New Fungal Metabolites from Aspergillus versicolor with Anti‐Inflammatory Activities

“…By the same protocol, the inhibitory effects of NO production in a dose dependent manner were observed in the LPS‐induced RAW24.7 cells treated by compounds 1 and 2 , respectively ( Figure , a ). Additional experiments indicated that compounds 1 and 2 down‐regulated the expression of proinflammatory cytokines including macrophage chemoattractant protein‐1 (MCP‐1), tumor necrosis factor (TNF‐ α ), and interleukin (IL‐6) in the LPS‐induced RAW264.7 cells after treatment with each compound at the doses of 10 and 1 μ m , respectively ( Figure , b – d ). In addition, a MTT assay revealed that compounds 1 and 2 did not reduce the cell viability of RAW264.7 macrophages up to a dose of 100 μ m , indicating that their inhibiting effects on LPS‐induced RAW24.7 cells were not due to cytotoxicity.…”

“…Thus, the peroxy bridge was oriented in the opposite face toward methylthiol group. The absolute configuration of C(2) was determined to be ( R ) based on the Δ δ ( R ) – ( S ) values calculated from ( R )‐ and ( S )‐MPA esters of 1 ( Figure ) by the Mosher method …”

Botryane Sesquiterpenoids, Cyclopentadepsipeptides, Xanthones, and Trichothecenes from Trichoderma oligosporum

“…1). Compounds 6-8 and 13-19 were identified as dehydrobotrydienol (6) [12], 12-hydroxydehydrobotrydienol (7) [12], hypocriol F (8) [13], 2,8-dihydroxy-3-methyl-9-oxoxanthene-1-carboxylic acid methyl ester (13) [14], preussochromone A (14) [15], preussochromone E (15) [15], roridin A (16) [16], roridin D (17) [17], roridin E (18) [18], and trichodermadienediol B (19) [19], respectively, by comparing their NMR, MS, and optical rotation data with literature values. The structure of 10 was identified as roseotoxin Z [20] by X-ray crystallographic analysis.…”

“…The structures of the new compounds 1-5, 9, and 11-12 were determined by extensive spectroscopic analysis. 13 C NMR (▶ Table 1), and HSQC data displayed four methyl signals, two oxygenated methylene signals at δ C/H 57.4/4.06 (d, J = 11.9 Hz) and 4.34 (d, J = 11.9 Hz) and δ C/H 71.0/ 3.29 (d, J = 10.7 Hz) and 3.33 (d, J = 10.7 Hz), and one oxygenated methine signal at δ C/H 68.4/3.63 (ddd, J = 11.6, 9.5, 3.6 Hz). The 1 H-1 H COSY correlations of H 3 -11-H-2-H 2 -3-H-4-H-5 (▶ Fig.…”

“…During our ongoing search for cytotoxic secondary metabolites from fungi [10], the EtOAc extract prepared from the solidsubstrate fermentation of Trichoderma oligosporum Z. X. Zhu & W. Y. Zhuang (Hypocreaceae) [11] was found to exhibit significant cytotoxicity against K562 cells (IC 50 150 µg/mL). Chemical investigation on the EtOAc extract of T. oligosporum led to the isolation of 19 secondary metabolites including botryanes (1)(2)(3)(4)(5)(6)(7)(8), cyclopetadepsipeptides (9-10), xanthones (11)(12)(13)(14)(15), and trichothecenes (16)(17)(18)(19). The isolation, structure elucidation, and cytotoxic activity of these metabolites are reported herein.…”