Trichodermatides A-D, four new polyketides from Trichoderma sp. XM-3.

Four new polyketides named trichodermatides A-D (1-4), along with five known analogues (5-9), were isolated from the fungus Trichoderma sp. XM-3. Their structures were elucidated on the basis of HRESIMS and NMR analyses, and their absolute configurations were determined by ECD comparison, 1H and 13C NMR calculation, DP4+ analysis, modified Mosher's method, and X-ray crystallography. Trichodermaketone D (9) showed mild antibacterial activity against Pseudomonas aeruginosa.

Terrusnolides A-D, new butenolides with anti-inflammatory activities from an endophytic Aspergillus from Tripterygium wilfordii.

Terrusnolides A-D (1-4), four butenolides were isolated from an endophytic Aspergillus from Tripterygium wilfordii. The structures of 1-4 were established by comprehensive spectroscopic analyses and electronic circular dichroism (ECD) calculation. It is interesting that 1 was a butenolide derived by a triple decarboxylation, while 2-4 were the metabolites with 4-benzyl-3-phenyl-5H-furan-2-one motif possessing an isopentene group fused to the benzene ring. In vitro anti-inflammatory effects of these isolates were evaluated in lipopolysaccharide (LPS)-stimulated RAW264.7 macrophages. 1-4 exhibited excellent inhibitory effects on the production of interleukin-1ß (IL-1ß), tumor necrosis factor-α (TNF-α), and nitric oxide (NO) in LPS-induced macrophages, comparable with the positive control (indomethacin). Those results indicated that, terrusnolides A-D might serve as new potential natural remedies for the treatment of inflammation.

Phenylacetylene-bearing 3,4-seco-cleistanthane diterpenoids from the roots of Phyllanthus glaucus.

Three new cleistanthane diterpenoids, phyllanglins A-C (1-3), a new natural product, 4-acetyl-bergenin (4), and three known compounds (5-7) were isolated from the roots of Phyllanthus glaucus. Their structures were elucidated by extensive spectroscopic data analyses and single-crystal X-ray diffraction. Phyllanglins A-C were unusual cleistanthane diterpenoids with phenylacetylene moieties, and a plausible biogenetic pathway was proposed to discuss the origins of them. All of the isolates were evaluated for their anti-inflammatory activities.

6,8-Di-C-methyl-flavonoids with neuroprotective activities from Rhododendron fortunei.

Six 6,8-di-C-methyl-flavonoids, (2R,3R)-6,8-di-C-methyl-5,7,4'-trihydroxyflavanonol 7-O-ß-d-gluco-pyranoside (1), (2R,3R)-6,8-di-C-methyl-5,7,4'-trihydroxyflavanonol 7-O-ß-d-xylopyranosyl(1→6)-ß-d-glucopyranoside (2), 6,8-di-C-methylkaempferol 7-O-ß-d-glucopyranoside (3), (2R)-farrerol (4a), (2R/2S)-farrerol 7-O-ß-d-glucopyranoside (5), and (2R/2S)-farrerol 7-O-ß-d-xylopyranosyl(1→6)-ß-d-glucopyranoside (6), and four known analogues, farrerol (4b), (2R,3R)-6,8-di-C-methyldihydrokae-mpferol (7), 6,8-di-C-methylkaempferol 7-O-ß-d-glucopyranoside (8), and 6,8-di-C-methylkaempferol (9), were isolated from the twigs and leaves of Rhododendron fortunei. The structures of compounds 1-9 were determined by spectroscopic analyses (HRESIMS, 1D and 2D NMR, and CD) and chemical methods. Compounds 1-9 were evaluated for their neuroprotective effects on the human neuroblastoma SH-SY5Y cells apoptosis induced by hydrogen peroxide (H2O2) and amyloid ß peptide (Aß), respectively. Compounds 1-3 and 5-9 exhibited significant neuroprotective effects against H2O2-induced SH-SY5Y cell apoptosis, and compound 8 exhibited the strongest activity with a improvement of cell viability by about 30% at the concentration of 10µM. Compounds 1-9 showed significant neuroprotective effects against Aß-induced SH-SY5Y cell apoptosis.

Enantiomeric Lignans and Neolignans from Phyllanthus glaucus: Enantioseparation and Their Absolute Configurations.

Eight pairs of enantiomeric neolignans, norlignans, and sesquineolignans (1a/1b-8a/8b), together with five known neolignans (9a/9b and 10-12), have been isolated from 70% acetone extract of the whole plants of Phyllanthus glaucus Wall. (Euphorbiaceae). The racemic or partial racemic mixtures were successfully separated by chiral HPLC using different types of chiral columns with various mobile phases. Their structures were elucidated on the basis of extensive spectroscopic data. The absolute configurations of 2a/2b were determined by computational analysis of their electronic circular dichroism (ECD) spectrum, and the absolute configurations of other isolates were ascertained by comparing their experimental ECD spectra and optical rotation values with those of structure-relevant compounds reported in literatures. Compounds 4a/4b featured unique sesquineolignan skeletons with a novel 7-4'-epoxy-8'-8''/7'-2'' scaffold, consisting of an aryltetrahydronaphthalene and a dihydrobenzofuran moiety. The planar structures of compounds 2, 3, 7, and 8 were documented previously; however, their absolute configurations were established for the first time in this study. The antioxidant activities of 1a/1b-8a/8b were evaluated using DPPH free radical scavenging assay, and the results demonstrated that compounds 1b and 3b showed potent DPPH radical scavenging activities with IC50 values of 5.987 ± 1.212 and 9.641 ± 0.865 µg/mL, respectively.

Neolignans with a Rare 2-Oxaspiro[4.5]deca-6,9-dien-8-one Motif from the Stem Bark of Cinnamomum subavenium.

Two pairs of racemic spirodienone neolignans with a rare 2-oxaspiro[4.5]deca-6,9-dien-8-one motif, named (±)-subaveniumins A (1) and B (2), were isolated from the bark of Cinnamomum subavenium. The chiral separation of the (+)-1, (-)-1, (+)-2, and (-)-2 enantiomers was accomplished via high-performance liquid chromatography on a chiral column. Their structures were elucidated using single-crystal X-ray diffraction and spectroscopic analyses (UV, IR, HRESIMS, and 1D and 2D NMR). The absolute configurations of the enantiomers were determined by comparing the experimental and calculated electronic circular dichroic spectra. The (+)-1, (-)-1, (+)-2, and (-)-2 enantiomers exhibited moderate inhibitory effects against NO production in RAW264.7 mouse macrophages induced by lipopolysaccharide, with IC50 values of 17.9, 5.6, 15.1, and 4.3 µM, respectively.

Salviprzols A and B, C21- and C22-terpenoids from the roots of Salvia przewalskii Maxim.

Two C21- and C22-terpenoids, salviprzols A (1) and B (2), together with 24 known compounds including 17 diterpenoids (3-19), a triterpenoid (20), and 6 phenolic derivatives (21-26), were isolated from the roots of Salvia przewalskii Maxim. Salviprzols A and B represented a new subtype of C23-terpenoids featured by an additional 2-oxopropyl moiety at C-12 and a rare γ-hydroxyl-α-methyl-α,ß-unsaturated-γ-lactone ring system. Their structures were elucidated by extensive spectroscopic analyses, and the structure of 2 was confirmed by a single-crystal X-ray diffraction crystallography. The cytotoxic activities of the new isolates were tested. A plausible biosynthetic pathway for 1 and 2 was also proposed.

Scapiformolactones A-I: germacrane sesquiterpenoids with an unusual Δ3-15,6-lactone moiety from Salvia scapiformis.

Nine germacrane sesquiterpenoids with an unusual Δ(3)-15,6-lactone moiety, scapiformolactones A-I (1-9), and one known seco-germacrane sesquiterpenoid, 3,7,11-trimethyldodeca-l,6,9-triene-3,11-diol (10), were isolated from whole plants of Salvia scapiformis Hance. Their structures were elucidated by spectroscopic methods including HR-ESIMS, IR, UV, NMR, and CD, as well as by quantum mechanical calculations and chemical transformations. Structures of compounds 1-3 were also confirmed by single-crystal X-ray diffraction analysis. Six germacrane 6,15-diol derivatives (11-16) were obtained by chemical transformation. Compounds 1-9 and 11-16 were evaluated for their in vitro immunomodulatory effects on T and B cells, as well as their in vitro cytotoxicity against five human cancer cell lines, HL-60, SMMC-7721, A-549, MCF-7, and SW480.

Cytotoxic ent-kaurane diterpenoids from Salvia cavaleriei.

Fifteen new ent-kaurane diterpenoids, compounds 1-15, and two known analogues, 4-epi-henryine A (16) and leukamenin E (17), were isolated from the whole plants of Salvia cavaleriei. The structures of the new compounds were established by spectroscopic methods, and their absolute configurations were determined by electronic circular dichroism and single-crystal X-ray diffraction analyses with Cu Kα radiation. Compounds 1-15 were evaluated for their cytotoxicity against five human cancer cell lines, HL-60, SMMC-7721, A-549, MCF-7, and SW480, as well as the noncancerous Beas-2B cell line. Compounds 1-10, 12, 14, and 15 showed broad-spectrum cytotoxicity, with compounds 1, 3, 6-10, 12, and 15 exhibiting more potent cytotoxicity than the positive control, cis-platin, with IC50 values ranging from 0.65 to 6.4 µM.

A new lignan glucoside from the whole plants of Salvia scapiformis.

Phytochemical investigation of the whole plants of Salvia scapiformis Hance afforded eight compounds, including one new lignan, (+)-8α-hydroxypinoresinol-8-O-[6''-O-(4'''-hydroxybenzoyl)]-ß-d-glucopyranoside (1), four known lignans, (+)-8α-hydroxy-pinoresinol-8-O-ß-d-glucopyranoside (2), (+)-8α-hydroxypinoresinol (3), (+)-pinoresinol (4), and (+)-medioresinol (5), and three known triterpenoids, ursolic acid (6), 4-epi-niga-ichigoside F1 (7), and niga-ichigoside F1 (8). Their structures were determined on the basis of extensive spectroscopic analyses and comparison with spectroscopic data in the literature. The absolute configuration of the new compound 1 was determined by chemical transformation and GC analysis.