Calvatianone, a Sterol Possessing a 6/5/6/5-Fused Ring System with a Contracted Tetrahydrofuran B-Ring, from the Fruiting Bodies of Calvatia nipponica

Abstract

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.

Anti-Adipogenic Polyacetylene Glycosides from the Florets of Safflower (Carthamus tinctorius)

“…The UV spectrum (Figure S8) of 2 was typical for an enediyne chromophore [16,17]. The 1 H (Figure S9) and 13 C NMR spectra of 2 (Table 1) showed a close resemblance to those of 8S-deca-4,6-diyne-1,8-diol-8-O-β-D-glucopyranoside [22], which was isolated as compound 5 in this study. The only slight difference in their chemical shifts was at the level of the glycosylated carbon group at C-1 and C-8, which was observed in compound 2 at δ C 69.1 (C-1, ∆δ C +7.8 ppm in CD 3 OD) and δ C 64.0 (C-8, ∆δ C −5.6 ppm in CD 3 OD) [22].…”

“…The IR spectrum showed absorptions attributable to the hydroxy (3396 cm −1 ) and acetylenic (2265 cm −1 ) groups. The 1 H (Figure S3) and 13 C NMR spectra of 1 (Table 1), combined with heteronuclear single quantum coherence (HSQC) and heteronuclear multiple bond correlation (HMBC) data, indicated the presence of a cis-configured ∆ S4-S6) revealed the strong similarity of 1 with bidenoside C [21], which was isolated as compound 3 in this study. The noticeable difference between the two compounds was that the NMR chemical shifts of C-10 in 1 showed a downfield shift owing to hydroxylation, which was confirmed based on the HMBC correlations between H-10 and C-8/C-9 (Figure 2).…”

“…Despite numerous evidences showing the beneficial effects of safflower on metabolism, the exact compounds responsible for the action and the mechanisms underlying their action remain undiscovered. As a part of our continued search for natural products with novel structural and/or biological properties [11][12][13][14][15], seven polyacetylene glycosides (1-7), including two new C10-polyacetylene glycosides, (8Z)-decaene-4,6-diyne-1,10-diol-1-O-β-D-glucopyranoside (1) and (8S)-deca-4,6-diyne-1,8-diol-1-O-β-D-glucopyranoside (2), were isolated from the extract of the florets of C. tinctorius by using LC-MS-UV-based chemical analysis. The structures of the new compounds were established by 1D and 2D NMR spectroscopic and high-resolution MS data analysis, and the absolute configurations of the sugar moiety were elucidated by chemical transformations followed by enzymatic hydrolysis.…”

“…1 H and13 C NMR data for compounds 1 and 2 in CD 3 OD. a Colorless amorphous gum; [a] 25 D − 18.5 (c 0.07, MeOH); UV (MeOH) λ max (log ε) 210 (3.03), 222 (3.46), 242 (0.68), 255 (0.98), 270 (1.21), 285 (0.91) nm; IR (KBr) ν max 3374, 2953, 2205, 1650, 1235, 1051 cm −1 ; 1 H (850 MHz) and 13 C (212.5 MHz) NMR data, see Table 1; ESIMS (positive-ion mode) m/z 351.1 [M + Na] + ; HRESIMS (positive-ion mode) m/z 329.1598 [M + H] + (calculated for C 16 H 25 O 7 , 329.1600).…”

Phytochemical Analysis of the Fruits of Sea Buckthorn (Hippophae rhamnoides): Identification of Organic Acid Derivatives

“…In this context, as a part of continuous research programs to discover structurally new bioactive compounds from diverse natural sources [ 13 , 14 , 15 , 16 , 17 , 18 , 19 ], our group has focused on the potential bioactive composition of H. rhamnoides fruits. In our recent study of H. rhamnoides fruits, we identified six chemical compounds, including one citric acid derivative, two flavonoids, one phenolic compound, and two megastigmane derivatives, which were evaluated for their anti-inflammatory effects by determining LPS-induced NO production in RAW 264.7 cells [ 20 ].…”