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Ochracines F–L (1–7), seven previously undescribed chamigrane and cadinane sesquiterpenoids, together with four known chamigranes were isolated from cultures of the wood-decaying fungus Steccherinum ochraceum HFG119. Ochracines F–L were structurally characterized by extensive analysis of HRMS and NMR spectroscopic data. The relative configurations were assigned through a combination of NOE correlations and J-based configuration analysis (JBCA), while the absolute configurations were determined by X-ray single-crystal diffraction, and calculated methods (ECD, [α], 13C NMR). All the new isolates were evaluated for their cytotoxicity against five human cancer cell lines HL-60, SMMC-7721, A549, MCF-7, and SW-480, and inhibitory activity on NO production in RAW 264.7 macrophages.

Eighteen new nor-isopimarane diterpenes, xylarinorditerpenes A-R (1-18), along with two previously reported compounds, 14α,16-epoxy-18-norisopimar-7-en-4α-ol (19) and the labdane-type diterpene agatadiol (20), were isolated from cultures of the fungicolous fungus Xylaria longipes HFG1018 isolated from the wood-rotting basidiomycete Fomitopsis betulinus. The structure elucidation and relative configuration assignments of 1-18 were accomplished by interpretation of spectroscopic data and through computational methods. The absolute configurations of 1, 4, and 16 were determined by single-crystal X-ray diffraction. Compounds 1-16 possess an 18- or 19-nor-isopimarane skeleton, and compounds 17 and 18 possess an 18,19-dinor-isopimarane skeleton. Compounds 2-5, 9, 14, 19, and 20 showed immunosuppressive activity but were devoid of cytotoxicity against the cell proliferation by concanavalin A-induced T lymphocytes and lipopolysaccharide-induced B lymphocytes, with IC50 values varying from 1.0 to 27.2 μM and from 16.1 to 51.8 μM, respectively.

Phytochemical investigation on the fermentation broth of the fungus Stereum hirsutum led to the isolation of ten steroids, including two previously unreported ones, namely steresterones A (1) and B (2). The semi-synthesis products 3a and 3b were prepared by reduction of the known compound 3 with NaBH4. Their structures and absolute configurations were established via 1D & 2D NMR spectroscopic analysis, and TDDFT/ECD calculations as well as single crystal X-ray diffraction analysis. The structure of 3 which harbored a 5β-H was confirmed by single crystal X-ray diffraction analysis for the first time. All the compounds reported in this study were evaluated for their cytotoxicity against five human cancer cell lines. Bioassay results revealed that 3, 4, 6―9 displayed significant anti-proliferative effects with IC50 values varying from 2.3 to 34.3 μM. The structure-activity relationships of 3, 3a, 3b were discussed.

A new cadinane-type sesquiterpenoid, microporotriol (1), together with four known compound, 5-methylresorcinol (2), (22E,24R)-ergosta-4,6,8(14),22-tetraen-3-one (3), (22E,24R)-ergosta-5,7,22-trien-3β-ol (4), (22E,24R)-5α,8α-epidioxy-ergosta-6,22-dien-3β-ol (5), were isolated from the fermentation broth of the wood decaying fungus Microporus affinis HFG829. The structures of the compounds were established by extensive spectroscopic methods, including 1D & 2D NMR, along with HRMS spectroscopic analysis. The relative configuration of 1 was confirmed by NMR calculation. Compound 1 was evaluated for the cytotoxicity against five human cancer cell lines.

Irpexolidal (1), a triterpenoid with an unprecedented carbon skeleton, along with its biogenetic-related compound irpexolide A (2), were isolated from the fruiting bodies of the medicinal fungus Irpex lacteus. Irpexolidal features a 6/5/6/5/6/5-fused polycyclic skeletal system which arises from the eburicane-type triterpene by a 6,7- seco-6,8- cyclo pattern. The structures of 1 and 2 were established by means of extensive spectroscopic techniques, ECD calculation, and DP4+ probability based on GIAO NMR chemical shift calculations. The plausible biosynthetic pathways for compounds 1 and 2 were proposed. Their biological activities were evaluated.

Extensive studies have revealed that triterpenoids, meroterpenoids, and polysaccharides are the main constituents of the well-known traditional Chinese medicinal mushroom Ganoderma. In this study, we report seven previously undescribed sesquiterpenoids, including six gymnomitranes (1–6) and a novel type of sesquiterpenoid (8), together with a polyketide (7) and a known steroid (9) from the fruiting bodies of Ganoderma lingzhi, a fungus used as traditional medicine and food supplement in East Asia for ages. The structures of 1–8 were deduced by analysis of spectroscopic data, X-ray single crystal diffractions and TDDFT/ECD calculations. Compound 8 possessed an unusual 14(7→6)-cuparane scaffold. Compound 9 exhibited weak cytotoxicity against the five human cancer cell lines HL-60, MCF-7, SW480, A549, and SMMC-7721 with IC50 values of 18.0–32.3 μM. A simple structure-activity-relationship (SAR) investigation by acetylating the 5-OH of 9 (9a) suggested that the 5-OH is essential for its cytotoxicity. Additionally, the biosynthetic pathways for compounds 2 and 8 are discussed.

A chemical investigation of the whole plant of traditional Chinese medicine, Chrysanthemum indicum L., led to the discovery of six guaianolide-type sesquiterpenoids 1–6 with a 1,10-splited skeleton. The structure of the new compound 1 was established by extensive analysis of UV, IR, MS, NMR and ECD data. Compounds 3–6 are mutually stereoisomers with four chiral centers and their absolute configurations were determined by comparison of ECD spectra. The anti-inflammatory effects of these isolates on lipopolysaccharide (LPS)-induced nitric oxide (NO) were investigated in RAW 264.7 cells. Results showed that most of the compounds displayed NO production inhibitory activities with IC50 values ranged from 3.54 to 8.17 μM.

Five new triterpenoids, irpeksins A-E (1-5), were isolated from fruiting bodies of the medicinal fungus Irpex lacteus. The structures as well as absolute configurations of the new compounds were established via extensive spectroscopic analysis, computational methods, and Cotton effects. Compounds 1-4 are featured by a scaffold of 1,10- seco- and ring B aromatic eburicane (24-methyllanostane), and compound 5 is characterized by a scaffold of 1,10-9,11- diseco- and ring B aromatic eburicane, which represents unprecedented cleavage patterns in the lanostane family. Compounds 1-5 showed significant inhibitory activity against NO production in LPS-activated RAW 264.7 macrophage cells with IC50 values varying from 2.2 to 19.6 μM.

Three previously undescribed cyathane-type diterpenoids, hericinoids A-C (1‒3) and three known analogues (4‒6) have been isolated from fermentation broth of Hericium erinaceus. Their structures of hericinoids A-C were determined by in-depth analyses of NMR spectra and HRESIMS. The absolute configurations of compounds 1 and 2 were determined by the ROESY spectra along with the DP4+ calculations based on quantum chemistry. Compounds 1–5 were inactive on the enhancement of NGF-induced neutrite outgrowth in PC-12 cells. Instead, compounds 2, 4, and 5 showed potent cytotoxicity against HL-60 cell lines with the IC50 values of 18.3, 8.9, and 0.5 μM, respectively. Compounds 4 and 5 showed moderate cytotoxicities against MCF-7 cell lines with the IC50 values ranging from 13.4 to 15.8 μM.

Two new pyridine derivatives climacomontaninates A–B (1–2), and a new sesquiterpenoid derivative climacomontanetate (3), together with twelve known compounds (4–15) were isolated from the culture extract of the fungal strain Climacocystis montana from the root bark of Paeonia ostii. The structures of these compounds were determined through spectroscopic methods such as NMR and HRMS. Moreover, we expound the absolute configuration of 1 using the organic synthesis method. The cytotoxicity against five human cancer cell lines of new compounds were evaluated by SRB assay.

Eight hetereocyclic compounds conflamides B–I with an unprecedented skeleton and their precursor conflamide A were isolated from the mushroom Albatrellus confluens. Their structures and absolute configurations were determined by use of NMR studies, total synthesis, and calculated ECD spectra. Conflamides D and E were found to exhibit potent inhibition against LPS-induced B lymphocyte cell proliferation with IC50 values 1.48 and 5.71 μM, respectively.

Four eburicane-type triterpenoids with malonyl modifications, namely irpexoates A–D (1–4), were isolated from the fruiting bodies of the medicinal fungus Irpex lacteus. The structures of the new compounds were established by extensive spectroscopic methods, including 1D and 2D NMR, HRESIMS spectroscopic analysis. Irpexoate B (2) displayed weak cytotoxicity against four human cancer cell lines (A-549, SMMC-7721, MCF-7, SW480) with IC50 values varying from 22.9 to 34.0 μM, and irpexoate D (4) showed weak cytotoxicity against the human cancer cell line SW480 with an IC50 value of 35.2 μM. Graphical Abstract Electronic supplementary material The online version of this article (10.1007/s13659-018-0160-3) contains supplementary material, which is available to authorized users.

Two new sesquiterpenes, daedaleanols A (1) and B (2), together with three known sesquiterpenes (3-5), were isolated from cultures of the basidiomycete Daedalea incana. Their structures were elucidated on the basis of extensive spectroscopic means. All compounds were tested for their cytotoxicities against three human cancer cell lines.

A scale-up fermentation of the fungus Boreostereum vibrans facilitated the isolation of six new vibralactone biogenesis-associated analogues, namely vibralactamide A (1), vibralactone T (2), 13-O-lactyl vibralactone (3), 10-O-acetyl vibralactone G (4), (11R,12R)- and (11S,12R)-vibradiol (5, 6). Their structures were established via extensive spectroscopic analyses, specific optical rotation comparison, and Snatzke’s method. The biosynthetic pathway for vibralactamide A was postulated. The absolute configuration of vibralactone B was revised by single crystal X-ray diffraction analysis. This work puts the divergent vibralactone biosynthesis pathway one step further and expands the structural diversity of vibralactone-associated compounds. Graphical Abstract Electronic supplementary material The online version of this article (10.1007/s13659-017-0147-5) contains supplementary material, which is available to authorized users.

Seven previously undescribed polyketides, namely childinins A-G, and one previously undescribed 8,14-seco-ergosterol, namely childinasterone A, were obtained from the fruiting bodies of Daldinia childiae. Their structures and absolute configurations were established via extensive spectroscopic analyses, single-crystal X-ray diffraction, and TDDFT/ECD calculations. Childinins A represents the first example of natural product possessing a previously undescribed 6H-naphtho[2,1-c]chromen-6-one scaffold. The single crystal X-ray diffraction of childinasterone A unambiguously determined the absolute configuration of a 8,14-seco-ergosterol skeleton. Childinins A, B, F and G (MIC90 54.9 μg⋅mL-1) showed anti-bacterial activities. Childinasterone A showed significant anti-NO activity (IC50 21.2 μM) and weak activities against SMMC-7721, MCF-7 and SW480 cell lines.

Betulactones A (1) and B (2) were isolated from the cultures of basidiomycete Lenzites betulinus. Betulactone A (1) was a novel highly oxygenated rigid spiro-g-lactone with the 5/5/6 ring system rarely found in fungal sources while betulactone B (2) was a highly degraded sterol. These structures were elucidated by extensive spectroscopic methods and computational ECD analysis. Compounds 1 and 2 were evaluated for their inhibitory activity of protein tyrosine phosphatase (PTP) 1B in vitro. (C) 2017 Phytochemical Society of Europe. Published by Elsevier Ltd. All rights reserved.

Investigation into the chemical diversity of Artemisia argyi led to the discovery of two new (1, 4) and four known (2-3, 5-6) sesquiterpenoids. The new structures were determined via extensive spectroscopic data, including IR, UV, MS, and NMR, and the absolute configurations of these compounds were elucidated by calculated ECD method. All isolates were tested for their inhibitory activity against NO production in RAW 264.7 macrophages, and the isolated sesquiterpenoids exhibited NO production inhibitory activity with IC50 values ranging from 1.91 to 36.52 μM.

Eighteen new lanostane-type triterpenoids, namely leucocontextins A-R (1-18) were isolated from the fruiting bodies of Ganoderma leucocontextum. Their structures were established by 1D and 2D NMR data in conjunction with HRESIMS/HREIMS, X-ray single crystal diffraction analysis. Compound 18 exhibited weak cytotoxicity against K562 and MCF-7 cell lines with IC50 of 20-30 μM.

(+)- and (−)-Ganodilactone (1), a pair of novel meroterpenoid dimers possessing a unique 5′H-spiro[chroman-4,2′-furan]-2,5′-dione ring system, along with their biogeneticly-related compound, ganomycin I (2), were discovered from the fruiting bodies of Ganoderma leucocontextum. The structures and absolute configurations were assigned with the aid of 1D and 2D NMR spectra, HRESIMS analysis and ECD calculations. (±)-, (+)-, and (−)-ganodilactone (1) showed pancreatic lipase inhibitory activities and exhibited the IC50 values as 27.3, 4.0, and 2.5 μM, respectively.

Matsudipeptides A (1) and B (2), two previously undescribed diketopiperazines with peroxy groups, were isolated from the fruiting bodies of the basidiomycete Tricholoma matsutake. These two compounds were featured by unusual scaffolds biogenetically related with cyclic dipeptide. Their structures were elucidated by analysis of spectroscopic data and calculated methods. Both the two compounds were evaluated for their cytotoxicity against five human cancer cell lines (HL-60, SMMC-7721, A549, MCF-7, and SW-480), and their inhibition on acetylcholinesterase.

This study features the isolation and identification of 12 lanostane-type triterpenoids, namely lepiotaprocerins A–L, 1–12, from the fruiting bodies of the Poland-collected edible mushroom Macrolepiota procera. The structures and the absolute configurations of the new compounds were ambiguously established by extensive spectroscopic analyses, ECD calculation, and single-crystal X-ray diffraction analyses. Structurally, lepiotaprocerins A–F, 1–6, are distinguished by the presence of a rare “1-en-1,11-epoxy” moiety which has not been previously described in the lanostane class. Biologically, lepiotaprocerins A–F, 1–6, displayed more significant inhibitions of nitric oxide (NO) production than the positive control L-NG-monomethyl arginine (L-NMMA) (IC50 47.1 μM), and lepiotaprocerins G–L, 7–12, showed various cytotoxicity potencies against a panel of human cancer cell lines. Compound 9 also displayed antitubercular activity against Mycobacterium tuberculosis H37Ra with a minimal inhibitory concentration (MIC...

Six previously undescribed 5,6-seco-tremulane analogues, together with two known ones, were isolated from the culture broth of the medicinal fungus Irpex lacteus HFG1102. The structures of the new compounds were elucidated via extensive spectroscopic methods, including NMR and HRMS spectroscopic analyses. Graphical Abstract Electronic supplementary material The online version of this article (10.1007/s13659-018-0157-y) contains supplementary material, which is available to authorized users.

Ten new highly oxygenated lanostane triterpenoids, stereinones A–J (1–10), were isolated from the fruiting bodies of the basidiomycete Stereum sp. Compounds 3 and 4 are structurally characterized as intact lanostane-type triterpenoids containing unusual 1,2-diketone functionality at C-11 and C-12, while compound 10 is a 24-methylene-lanostane. The structures of these new compounds were established based on detailed 1D and 2D NMR spectroscopic analyses, along with quantum chemical NMR calculations. All isolates were evaluated for their in vitro cytotoxicities against five human tumor cell lines (including HL-60, A-549, SMMC-7721, MCF-7, and SW480 cell lines). Compound 4 showed moderate cytotoxic activities against tumor cell lines SMMC-7721 and SW480 with IC50 values of 9.1 and 9.8 μM, respectively.

Molecular identification suggested an edible mushroom, which was previously named as Craterellus odoratus should be revised as Montagnula donacina. A chemical re-investigation of the culture broth of this fungus resulted in the isolation of four rare tetracyclic bergamotane-type sesquiterpenoids, namely donacinolides A and B, donacinoic acids A and B, and three cadinane-type ones, namely donacinols A–C and a meroterpenoid (Z)-4-hydroxy-3-(3-hydroxy-3-methylbut-1-en-1-yl)benzoic acid. Their structures were established via extensive spectroscopic methods, single crystal X-ray diffraction analysis, and computational methods. (Z)-4-Hydroxy-3-(3-hydroxy-3-methylbut-1-en-1-yl)benzoic acid showed antibacterial activity against Staphylococcus aureus.

Ochracines A-E, five previously undescribed norsesquiterpenes featured by unusual scaffolds biogenetically related to chamigrane, were isolated from the cultures of Steccherinum ochraceum. Ochracines A (1) and B (2) represent the first examples of norsesquiterpenes with an unprecedented 1,2-6,7-diseco-1,8-cyclochamigrane scaffold. Ochracines C-D (3–5) possess an unusual 1,2-6,7-diseco-chamigrane skeleton. Their structures were elucidated by analysis of spectroscopic data. The absolute configuration of ochracine A (1), and the relative configuration of ochracine B (2) were determined by ECD and/or NMR calculations. The biosynthetic pathways for the norsesquiterpenes were proposed. All isolates were evaluated for their cytotoxicity against the five human cancer cell lines HL-60, SMMC-7721, A549, MCF-7, and SW-480.

A variety of novel natural products with significant bioactivities are produced by the basidiomycete Boreostereum vibrans. In the present study, we describe 16 novel natural oximes and oxime esters with a vibralactone backbone, vibralactoximes, which were isolated from the scale‐up fermentation broth of B. vibrans. Their structures were determined through extensive spectroscopic analyses. These compounds represent the first oxime esters from nature. The hypothetical biosynthetic pathway of these compounds was also proposed. Seven compounds exhibited significant pancreatic lipase inhibitory activity, while ten compounds exhibited cytotoxicities against five human cancer cell lines (HL‐60, SMMC‐7721, A‐549, MCF‐7, and SW480), with IC50 values comparable with those of cisplatin.

Six new lanostane-type triterpenoids, namely leucocontextins S–X (1–6), together with twelve known compounds, were isolated from the fruiting bodies of Ganoderma leucocontextum. Their structures were established by MS and NMR data. Graphical Abstract Electronic supplementary material The online version of this article (doi:10.1007/s13659-016-0089-3) contains supplementary material, which is available to authorized users.