Three new macrocyclic trichothecenes (1−3) and five known related compounds (4−8) were isolated from the MeOH extract of a plate culture of the fungus Podostroma cornu-damae, a deadly poisonous mushroom. Miophytocen D (1) is a rearranged macrocyclic type D trichothecene, featuring a bicyclo-[6.5]dodecahydrocyclopenta[b]chromene scaffold, and the structures of new compounds (1−3) were delineated by the combination of 1D and 2D NMR spectroscopic experiments and HRESIMS, modified Mosher's esterification, and quantum chemical ECD calculations. The isolated compounds (1−8) were evaluated for cytotoxicity against four human breast cancer cell lines (Bt549, HCC70, MDA-MB-231, and MDA-MB-468). Compounds 4, 6, and 8 exhibited significant cytotoxic effects against the breast cancer cell lines, with IC 50 values in the range of 0.02−80 nM, which is stronger than doxorubicin, the positive control, and a structure−activity relationship was suggested.Podostroma cornu-damae is a lethal toxic mushroom belonging to the Hypocreaceae family and contains fatal trichothecenes, a large family of chemically related mycotoxins that present a potential threat to public health throughout the world. 1 The mushroom, which is widely distributed in Japan, China, and East Asia, is known as the red deer's horn mushroom due to its exceptional deer-horn-like appearance. 2 Because the shape of P. cornu-damae resembles immature Ganoderma lucidum and Cordyceps medicinal mushrooms, fatal poisonings have occurred accidentally from misunderstandings involving these mushrooms. 2,3 In Japan, 13 cases of accidental intoxication of P. cornu-damae were reported from 1983 to 2008, including two deaths after ingesting only a few centimeters of its fruiting body. 2,3 In Korea, of two people who ate boiled fungus, one person died because of multiorgan failure in spite of aggressive medical intervention, and the other improved after conservative management for one month. 1,4 The early symptoms of poisoning are vomiting, dehydration, and diarrhea. After approximately 3 days, anuria, hypotension, polypnea, leukopenia, thrombocytopenia, and disturbance of consciousness have been reported. 2,3 There is only one report on the chemical investigation of toxic metabolites from P. cornu-damae, 5 where satratoxin H 12′,18′-diacetate, satratoxin H 12′-acetate, and satratoxin H 13′-acetate have been identified as new macrocyclic trichothecenes. All of the isolated macrocyclic

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Calvatia nipponica is an extremely rare mushroom with a limited number of studies on its chemical components and biological activities published. Here we report the isolation of a novel sterol, calvatianone (1), possessing a 6/5/6/5-fused ring system with a contracted tetrahydrofuran B-ring, and four known steroids (2–5) from the fruiting bodies of C. nipponica. The structure of calvatianone including its absolute configuration was determined by NMR spectroscopic analyses, HR-ESIMS, gauge-including atomic orbital NMR chemical shift calculations, and ECD calculations. Ergosterol peroxide (3) and cyathisterol (4) suppressed the cell viability increase induced by 17β-estradiol in MCF-7 breast cancer cell lines, suggesting a possible approach for these compounds to serve as ERα antagonists.

A styrylpyrone-fused ergosterol derivative, ergopyrone (1), was isolated and structurally characterized from a mushroom, Gymnopilus orientispectabilis, along with five biosynthetically related metabolites (2–6). Compound 1 features an unprecedented hexacyclic 6/5/6/6/6/5 skeleton that would be formed from ergosterol and styrylpyrone precursors via [3 + 2] cycloaddition. The chemical structure of 1 was elucidated by conventional spectroscopic and spectrometric data analysis coupled with computational methods including DP4+ probability and ECD simulation and an NOE/ROE-based interproton distance measurement technique via peak amplitude normalization for the improved cross-relaxation (PANIC) method. Plausible biosynthetic pathways of 1–6 are proposed, and compound 6 significantly regulated lipid metabolism in adipocytes through the upregulation of the mRNA expression of Adipsin, Fabp4, SREBP1, and ATGL.