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Chromones from Cnidium monnieri
Abstract
Four new chromones, cnidimol C–F, along with cnidimol A, cnidimol B and karenin were isolated from the aerial parts of Cnidium monnieri. The structures of the new chromones were determined to be 5,7-dihydroxy-2-hydroxy-methylchromone, 5,7-dihydroxy-6-[(2Z)-3-hydroxymethyl-2-butenyl]-2-hydroxymethylchromone, 5,7-dihydroxy-6-[2-hydroxy-3-methyl-3-butenyl]- 2-hydroxymethylchromone and 5,8-dihydroxy-2-hydroxymethyl-8-methyl-4H,9H-pyrano [3,2-h][1]benzoxepin-4-one.
... The given values fit to esculetin, but were incomplete and wrong for the proposed chromone-derivative. The structure elucidation was done by comparison with the literature data; therefore it should be mentioned that obviously correct 13 C-NMR data for compound 5 were already published in [34]. the details of the structure proofs based on 13 C-NMR spectroscopy. ...
... The given values fit to esculetin, but were incomplete and wrong for the proposed chromone-derivative. The structure elucidation was done by comparison with the literature data; therefore it should be mentioned that obviously correct 13 C-NMR data for compound 5 were already published in [34]. [33] together with the published 13 C-NMR data (green, signal assigned by author, and yellow, signal exchangeable assigned) and the differences between experimental and predicted values (cred > 10 ppm, yellow < 10 ppm and >5 ppm, green < 5 ppm). ...
A systematic investigation of the experimental 13C-NMR spectra published in Molecules during the period of 1996 to 2015 with respect to their quality using CSEARCH-technology is described. It is shown that the systematic application of the CSEARCH-Robot-Referee during the peer-reviewing process prohibits at least the most trivial assignment errors and wrong structure proposals. In many cases, the correction of the assignments/chemical shift values is possible by manual inspection of the published tables; in certain cases, reprocessing of the original experimental data might help to clarify the situation, showing the urgent need for a public domain repository. A comparison of the significant key numbers derived for Molecules against those of other important journals in the field of natural product chemistry shows a quite similar level of quality for all publishers responsible for the six journals under investigation. From the results of this study, general rules for data handling, data storage, and manuscript preparation can be derived, helping to increase the quality of published NMR-data and making these data available as validated reference material.
... Cnidium monnieri (L.) Cusson (Umbelliferae) is an annual herb distributed in China, India, Russia, Korea, Mongolia, Vietnam, Europe, and North America [1,2]. Chromones [3,4], coumarins [5][6][7][8][9], benzofurans [10], and monoterpenoids [11], and their derivatives were isolated from this plant in previous studies. Many of these compounds were found to exhibit antidermatophytic [9], anti-scratching [5], and cytotoxic [8] activities. ...
... The water layer was further extracted with n-BuOH, and the n-BuOH-soluble part (fraction B, 132 g) and the water-solubles (fraction C, 128 g) were separated. Fraction A (110 g) was chromatographed on silica gel (70-230 mesh, 5.1 kg), eluting with n-hexane, gradually increasing the polarity with acetone to give 12 fractions: A1 (5 L, n-hexane), A2 (4 L, n-hexane/acetone, 99:1), A3 (4 L, n-hexane/acetone, 95:1), A4 (5 L, n-hexane/acetone, 90:1), A5 (4 L, n-hexane/acetone, 80:1), A6 (4 L, n-hexane/acetone, 70:1), A7 (4 L, n-hexane/acetone, 50:1), A8 (6 L, n-hexane/acetone, 30:1), A9 (4 L, n-hexane/acetone, 10:1), A10 (5 L, n-hexane/acetone, 3 ...
The fruit of Cnidium monnieri is commercially used as healthcare products for the improvement of impotence and skin diseases. Three new coumarins, 3'-O-methylmurraol (1), rel-(1'S,2'S)-1'-O-methylphlojodicarpin (2), and (1'S,2'S)-1'-O-methylvaginol (3), have been isolated from the fruits of C. monnieri, together with 14 known compounds (4-17). The structures of these new compounds were determined through spectroscopic and MS analyses. Compounds 1, 4-12, and 14-17 exhibited inhibition (IC50 ≤ 7.31 µg/mL) of superoxide anion generation by human neutrophils in response to formyl-l-methionyl-l-leucyl-l-phenylalanine/cytochalasin B (fMLP/CB). Compounds 7, 9-11, 15, and 17 inhibited fMLP/CB-induced elastase release with IC50 values ≤7.83 µg/mL. This investigation reveals that bioactive isolates (especially 6, 7, 14, and 17) could be further developed as potential candidates for the treatment or prevention of various inflammatory diseases.
... Cnidii monnieri Fructus (CmF), dried fruit of Cnidium monnieri (L.) Cusson (Umbelliferae), has been used for treatment of pain in female genitalia, impotence and suppurative dermatitis and is soaked in rice wine as a tonic agent in China [1]. The fruit contains coumarins, chromones, essential oil, terpenoids, glycosides [2], [3], [4], [5]. Moreover, pharmacological studies of the fruit have shown that coumarins are the active principle constituents [2]. ...
... Fractions were combined on the basis of thin layer chromatography and evaporated under reduced pressure to give each compound. All structures were estimated by optical rotation, GC-MS, 1 H-and 13 C-NMR including 2D-NMR techniques and also by comparison with the data of authentic compounds [2], [3], [4], [5]. The purity of each compound was determined by HPLC and was shown to exceed 99.5 %. ...
Cnidii monnieri Fructus [CmF; Cnidium monnieri (L.) Cusson] is used as a tonic agent in traditional Chinese medicine. In a previous Chinese herb-cytotoxicity screening test, the ethanol extract of CmF exhibited strong effects on human leukemia (HL-60), cervical carcinoma (HeLa) and colorectal carcinoma (CoLo 205) cells. Then, the CmF extract was subjected to silica gel column chromatography and recrystallization to give five coumarins: osthol, imperatorin, bergapten, isopimpinellin, and xanthotoxin. Among these compounds, osthol showed the strongest cytotoxic activity on tumor cell lines. The structure-activity relationship established from the results indicated that the prenyl group has an important role in the cytotoxic effects. However, imperatorin showed the highest sensitivity to HL-60 cells and the least cytotoxicity to normal PBMCs. Osthol and imperatorin both caused apoptotic bodies, DNA fragmentation, and enhanced PARP degradation in HL-60 cells by biochemical analysis. These results indicate that osthol and imperatorin can induce apoptosis in HL-60 cells. Therefore, osthol and imperatorin are cytotoxic marker substances in the fruits of Cnidium monnieri.
... Cnidii Monnieris Fructus showed stronger inhibitory effects on furin-like activity than Cnidii rhizome (IC 50 > 50 µg/mL). Cnidii Monnieri Fructus (Jashoshi in Japanese) has been traditionally used to treat osteoporosis, sexual dysfunction, asthma, and skin ailments [27]. Cnidium monnieri Cusson contains several compounds, such as bergapten, imperatorin, osthole, and xanthotoxin [28]. ...
The spike (S) protein of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) contains a cleavage motif R-X-X-R for furin-like enzymes at the boundary of the S1/S2 subunits. The cleavage of the site by cellular proteases is essential for S protein activation and virus entry. We screened the inhibitory effects of crude drugs on in vitro furin-like enzymatic activities using a fluorogenic substrate with whole-cell lysates. Of the 124 crude drugs listed in the Japanese Pharmacopeia, aqueous ethanolic extract of Cnidii Monnieris Fructus, which is the dried fruit of Cnidium monnieri Cussion, significantly inhibited the furin-like enzymatic activities. We further fractionated the plant extract and isolated the two active compounds with the inhibitory activity, namely, imperatorin and osthole, whose IC50 values were 1.45 mM and 9.45 µM, respectively. Our results indicated that Cnidii Monnieris Fructus might exert inhibitory effects on furin-like enzymatic activities, and that imperatorin and osthole of the crude drug could be potential inhibitors of the motif cleavage.
... Cnidii monnieri Fructus are the dried fruits of Cnidium monnieri (L.) Cusson. C. monnieri Fructus is an important traditional Chinese medicine formulation and used to treat osteoporosis, sexual dysfunction, asthma and skin ailments (Baba et al., 1992). Osthole (also known as "osthol") is found in various plants, including Cnidium monnieri. ...
Inhibition of activated macrophages is an alternative therapeutic strategy for asthma. We investigated whether a coumarin compound, osthole, isolated from Cnidium monnieri (L.) Cuss, alleviated macrophage activation in vivo and in vitro. Osthole could reduce expression of a marker of activated macrophages, cluster of differentiation (CD)206, in an ovalbumin-challenge model of asthma in mice. Osthole could also inhibit infiltration of inflammatory cells, collagen deposition and production of proinflammatory cytokines [interleukin (IL)-1β, tumor necrosis factor-ɑ, macrophage migration inhibitory factor (MIF)] in asthmatic mice. In vitro, expression of phosphorylated-IĸBɑ, MIF and M2 cytokines (Ym-1, Fizz-1, arginase-1) in IL-4-induced macrophages decreased upon exposure to the NF-ĸB inhibitor MG-132. In our short hairpin (sh)RNA-MIF-knockdown model, reduced expression of M2 cytokines was detected in the IL-4 + shRNA-MIF group. Osthole could attenuate the proliferation and migration of an IL-4-induced rat alveolar macrophages line (NR8383). Osthole could reduce IL-4-induced translocation of nuclear factor-kappa B (NF-ĸB) in NR8383 cells. Collectively, our results suggest that osthole ameliorates macrophage activation in asthma by suppressing the NF-ĸB/MIF signaling pathway, and might be a potential agent for treating asthma.
... Compounds 1-5 were identified by a combination of spectroscopic analysis and comparison with previously reported data as heterocarpin (1), cnidimol A (2), cnidimoside A (3), isopimpinellin (4) and hyunganol II (5), respectively [6][7][8][9]. ...
The inhibitory effect of three chromones 1-3 and two coumarins 4-5 on the production of nitric oxide (NO) was evaluated in LPS-induced RAW 264.7 macrophage cells. Among the compounds tested heterocarpin (1), a furochromone, significantly inhibited its production in a dose-dependent manner. In addition, heterocarpin suppressed prostaglandin E2 (PGE2) production and expression of cytokines such as inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), tumor necrosis factor-α (TNF-α), interleukin-1β (IL-1β) and interleukin-6 (IL-6).
Natural products containing oxepinochromene motifs were first isolated from natural sources in 1960s. Natural oxepinochromenes are relatively rare and their source is limited to several endophytic and endolichenic fungi or higher plants. The importance of natural oxepinochromene derivatives lies in their promising biological activity. They exhibit a wide range of activities such as antibacterial, anticancer, anti-inflammatory or antifungal. Consequently, their synthesis has attracted significant interest. This review discusses the source, biosynthesis, biological activity, reactions as well as the total synthesis of oxepinochromene derivatives, belonging to the xanthone, terpenoid and flavone groups of phenolic secondary metabolites.
This study aimed to determine the effect of synbiotic Musa acuminata skin extract (MASE) and Streptococcus salivarius K12 (K12) on Candida species biofilm formation. Liquid chromatography quadrupole time-of-flight (LC-Q-TOF-MS) was conducted to characterize MASE. To determine the effect of synbiotic on Candida biofilm, 200 µL of RPMI-1640 containing Candida, K12, and MASE were pipetted into the same well and incubated at 37 °C for 72 h. A similar protocol was repeated with K12 or MASE to determine the probiotic and prebiotic effects, respectively. Dimorphism, biofilm biomass, and Candida total cell count (TCC) were determined. A total of 60 compounds were detected in MASE. C. albicans (ALT5) and Candida lusitaniae exhibited the highest reduction in biofilm biomass when co-cultured with prebiotic (77.70 ± 7.67%) and synbiotic (97.73 ± 0.28%), respectively. All Candida spp. had decreased TCC and hyphae when co-cultured with synbiotic. In conclusion, MASE and K12 inhibit Candida biofilm formation.
Bioassay-guided fractionation of extracts derived from solid cultures of a Herbidospora daliensis originating from Taiwan led to the isolation of five new compounds, for which we propose the name herbidosporadalins A–E (1–5), one isolated for the first time, herbidosporadalin F (6), together with two known compounds (7 & 8). Their structures were elucidated by spectroscopic analyses, including 1D- and 2D-NMR experiments with those of known analogues, and on the basis of HR-EI-MS mass spectrometry, their anti-inflammatory activities were also evaluated. Of these isolates, herbidosporadalin A (1), B (2), F (6) and G (8) showed NO inhibitory activity, with IC50 values of 11.8 ± 0.9, 7.1 ± 2.9, 17.8 ± 1.7, and 13.3 ± 6.5 μM, stronger than the positive control quercetin (IC50 = 36.8 ± 1.3 μM). To the best of our knowledge, this is the first report on 3,4-seco-friedelane metabolites (5, 6 & 8) from the genus Herbidospora.
Two new chromones named cnidimol G (1) and cnidimol H (2), one new coumarin, 7-methoxy-8-(3-methoxy-3-methyl-2-oxobutyl)coumarin (3), and twenty known compounds were isolated from MeOH extract of the fruit of Cnidium monnieri (L.) Cusson. The structures of compounds were elucidated by extensive spectroscopic analyses including 1 D and 2 D NMR, HRESIMS, IR and UV. Anti-inflammatory activity of the selected isolated compounds were evaluated. Compounds 1 and 8 exhibited inhibitory activities against nitric oxide production.
Two new prenylated chromones, artoheterophines A (1) and B (2), five known prenylated chromones (3–7), as well as five known biogenetically related prenylated flavonoids (8–12) were isolated and characterized from the stems and leaves of A. heterophyllus. Their chemical structures were unambiguously determined through comprehensive spectral data analyses. The antiproliferative and anti-inflammatory effects of all these isolated prenylated chromones and flavonoids were evaluated in vitro. As a result, compounds 1–12 showed notable inhibitory effects against various human cancer cell lines with IC50 values ranging from 0.36 ± 0.02 to 22.09 ± 0.16 μM. Meanwhile, compounds 1–12 exhibited significant inhibitory activities on nitric oxide (NO) production holding IC50 values in the range of 0.48 ± 0.05 to 19.87 ± 0.21 µM. These research results suggest that the isolation and characterization of these prenylated chromones (1–7) and flavonoids (8–12) holding significant antiproliferative and anti-inflammatory activities could be significant to the discovery and development of new natural anti-tumor and anti-inflammatory drugs. The findings also provides a phytochemical evidence for further development and utilization of the stems and leaves of A. heterophyllus in health and pharmaceutical products.
Chromones are naturally occurring phenolic compounds that are universally present in a healthy human diet. To date, thousands of chromone derivatives, including chromone glycosides have been discovered, both from natural and synthetic origin. Many plant genera, including Aloe, Aquilaria, Cassia, Hypericum and Polygonum, are rich sources of chromones. Several genera of fungi, such as Aspergillus, Mycoleptodiscus, Orbiocrella, and Penicillium produce bioactive chromones. This class of compounds is mainly associated with anti-oxidant, antimicrobial, anticancer and anti-inflammatory activities. Various in vitro, in vivo and clinical studies have established the role of chromones in alleviating allergies, reducing oxidative damage, inhibiting cancer, infections and inflammation, and for treating neurological and psychiatric disorders. This review focuses mainly on natural chromones, and elaborates on their nutritional benefits, pharmacological activities, and mechanisms of action. Various scientific databases, including PubMed, Scopus and Google Scholar, were used to find relevant literature on chromones covering all available literature up to, and including the year 2019. This critical analysis of completed research regarding the nutraceutical properties of various chromone derivatives may provide new insight to scientists working in related fields.
Three new caryophyllane-type sesquiterpenoids, linariophyllenes A-C (1-3), two new hamamelitol derivatives, linaritols A (4) and B (5), two new chromones, linariosides A (6) and B (7), and three known chromones, cnidimol C (8), monnieriside A (9), and undulatoside A (10), were identified from the aerial parts of Evolvulus linarioides. The structures of these compounds were elucidated by NMR, MS, and IR data. The absolute configurations of compounds 1-5 and 7 were established via electronic circular dichroism data. The anti-inflammatory potential of compounds 1-5 and 7-10 was evaluated by determining their ability to inhibit the production of nitric oxide (NO) and proinflammatory cytokine IL-1β by stimulated J774 macrophages. Compounds tested at noncytotoxic concentrations inhibited NO production by macrophages, exhibiting IC50 values between 17.8 and 66.2 μM, and inhibited IL-1β production by stimulated macrophages by 72.7-96.2%.
Artocarpus heterophyllus (jack tree) is an evergreen fruit tree belonging to the genus Artocarpus (Moraceae), which is widely distributed in subtropical and tropical regions of Asia. Its fruits (jackfruit), well-known as the world's largest tree-borne fruit, are being consumed in our daily diets as a very popular tropical fruit throughout the world and have been confirmed to hold various health benefits. In this study, five new prenylated chromones, artocarheterones A-E (1-5), as well as seven known prenylated chromones (6-12) were purified and isolated from the ripe fruits of A. heterophyllus (jackfruit). Their chemical structures were determined through comprehensive spectroscopic methods. This is the first report on prenylated chromones isolated from A. heterophyllus. The anti-HIV-1 effects of all isolated chromones were assessed in vitro. As a result, prenylated chromones (1-12) showed remarkable anti-HIV-1 effects with EC50 values ranging from 0.09 to 9.72 μM. These research results indicate that the isolation and characterization of these prenylated chromones with remarkable anti-HIV-1 activities from the ripe fruits of A. heterophyllus could be significant to the discovery and development of new anti-HIV-1 drugs.
Cnidium monnieri (L.) Cusson (CMC) is a traditional Chinese herbal medicine that has been widely grown and used in Asia. It is also known as “She chuang zi” in China (Chinese: 蛇床子), “Jashoshi” in Japan, “Sasangia” in Korea, and “Xa sang tu” in Vietnam. This study aimed to provide an up-to-date review of its phytochemistry, ethnopharmacology, pharmacokinetics, and toxicology. All available information on CMC was collected from the Encyclopedia of Traditional Chinese Medicines, PubMed, EMBASE, ScienceDirect, Scopus, Web of Science, and China Network Knowledge Infrastructure. The updated chemical structures of the compounds are those ones without chemical ID numbers or references from the previous review. A total of 429 chemical constituents have been elucidated and 56 chemical structures have been firstly identified in CMC with traceable evidence. They can be categorized as coumarins, volatile constituents, liposoluble compounds, chromones, monoterpenoid glucosides, terpenoids, glycosides, glucides, and other compounds. CMC has demonstrated impressive potential for the management of various diseases in extensive preclinical research. Since most of the studies are overly concentrated on osthole, more research is needed to investigate other chemical constituents.
Three pairs of racemic dimers, (±)-cnidimonins A–C (1–3), were isolated from the fruits of Cnidium monnieri. They represent novel hybrid-dimerization patterns of coumarin skeleton with structurally diverse units (flavonol, benzofuran, and chromone) via an unprecedented terminal chiral carbon of prenyl. The absolute configurations of the enantiomers were determined by electronic circular dichroism (ECD). To investigate their bioactivities in depth, (±)-cnidimonins A–C (1–3) were synthesized. The racemic mixture (±)-1 exhibited stronger antiviral activity against HSV-1 (IC50: 1.23 μM) than its corresponding optically pure enantiomers.
Osthole, an active coumarin extracted from the dried fruits of Cnidium monnieri (L.) Cusson, is known to possess a variety of pharmacological activities. In the present study, we investigated and illuminated the mechanisms underlying the protective effects of osthole in an experimental model of allergic asthma. Our results show that osthole treatment significantly reduced the OVA-induced increase in serum IgE and inflammatory cytokines (IL-4, IL-5, IL-13) in bronchoalveolar lavage fluid (BALF), and decreased the recruitment of inflammatory cells in BALF and the lung. It also effectively attenuated goblet cell hyperplasia and mucus overproduction in lung tissue. In addition, western blot analysis demonstrated that osthole blocked NF-κB activation, which may be associated with a reduction in inflammatory cytokine production. These data suggest that osthole attenuated OVA-induced allergic asthma inflammation by inhibiting NF-κB activation. The present study identified the molecular mechanisms of action of osthole, which support the potential pharmaceutical application of osthole treatment for asthma and other airway inflammation disorders.
Objective
To identify the coumarins constituents in Cnidium monnieri and classify ten samples into three groups and this helpful chemical information could be used for the further pharmacological and clinical study on C. monnieri.
Methods
Qualitative analysis of coumarins in C. monnieri was detected by UHPLC-ESI-Q-TOF/MS. Quadrupole TOF/MS in either full scan mode or extracted ion mode was used for the qualitative analysis of the constituents. Relative peak area of each component was used for the hierarchical cluster analysis.
Results
According to UHPLC-ESI-QTOF-MS data, chemical structures of 28 coumarins in the fruits of C. monnieri were identified, including 19 simple coumarins, seven linear coumarins, and two angular coumarins. Among these constituents, ten coumarins were firstly identified in C. monnieri. In addition, hierarchical cluster analysis suggested that C. monnieri from different regions could be classified into four groups, and this clustering was correlated to the distribution significantly, Xuzhou could be regarded as the genuine producing area.
Conclusion
UHPLC-ESI-Q-TOF-MS is a viable method for qualitative analysis and quality evaluation of coumarins from the fruit of C. monnieri. Coumarins in C. monnieri exists intra-species variance, which indicates significant meaning for the quality control and choice of famous region drug for C. monnieri in the clinic medication.
A furochromone, heterocarpin (1), was isolated from the halophyte Corydalis heterocarpa, along with four known compounds (2-5), which were obtained for the first time from this genus. The chemical structures of these compounds were determined by extensive 2-D NMR experiments and by comparison with the data reported in the literature. Compound 1 showed significant cytotoxic activities against four human cancer cells, AGS (human gastric cancer), HT-29 (human colon cancer), HT-1080 (human fibrosarcoma) and MCF-7 (human breast carcinoma). According to the cytotoxicity results, the mechanism behind the cytotoxic presence of compound 1 on AGS cells was investigated through the mRNA and protein levels of apoptotic pathway factors such as p21, p53, Bax, Bcl-2, XIAP, and caspases-3 and -9. The results indicated that heterocarpin (1) showed the cytotoxic effect on cancer cells by inducing apoptosis via regulated Bax-Bcl-2 ratio, overproduced caspases and suppressed XIAP. The inhibition of NFκB and activation of JNK and ERK pathways were also observed in the presence of heterocarpin (1). Therefore, heterocarpin and its source C. heterocarpa were suggested to be utilized as a functional food with potential pro-apoptotic activity against cancer cells.
Osthole, an active coumarin isolated from Cnidium monnieri (L.) Cusson, has long been used in China as an antipruritic herbal medicine; however, the antipruitic mechanism of osthole is unknown. We studied the molecular mechanism of osthole in histamine-dependent itch by behavioral test, Ca2+ imaging, and electrophysiological experiments. First, osthole clearly remitted the scratching behaviors of mice induced with histamine, HTMT, and VUF8430. Second, in cultured dorsal root ganglion (DRG) neurons, osthole showed a dose-dependent inhibitory effect to histamine. On the same neurons, osthole also decreased the response to capsaicin and histamine. In further tests, the capsaicin-induced inward currents were inhibited by osthole. These results revealed that osthole inhibited histamine-dependent itch by modulating TRPV1 activity. This study will be helpful in understanding how osthole exerts anti-pruritus effects and suggests that osthole may be a useful treatment medicine for histamine-dependent itch.
Cnidium monnieri (L.) Cuss., an annual plant of the Umbelliferae species is one of the most widely used traditional herbal medicines and its fruits have been used to treat a variety of diseases in China, Vietnam, and Japan. The aim of this review is to provide an up-to-date and comprehensive analysis of the botany, traditional uses, phytochemistry, pharmacology, toxicity and contraindication of Cnidium monnieri (L.) Cuss. and to provide future directions of research on this plant. To date, 350 compounds have been isolated and identified from Cnidium monnieri (L.) Cuss., including the main active constituent, coumarins. In vitro and in vivo studies suggest that osthole and other coumarin compounds possess wide range of pharmacological properties for the treatment of female genitals, male impotence, frigidity, skin-related diseases, and exhibit strong antipruritic, anti-allergic, antidermatophytic, antibacterial, antifungal, anti-osteoporotic effects. Although coumarins have been identified as the main active constituents responsible for the observed pharmacological effects, the molecular mechanisms of their actions are still unknown. Therefore, further studies are still required to reveal the structure-activity relationship of these active constituents. In addition, toxicological and clinical studies are also required to provide further data for pharmaceutical use.
Hypocrolide A (1), a botryane metabolite with a new hexacyclic skeleton, was isolated from cultures of the entomogenous fungus Hypocrea sp. The proposed structure was confirmed by X-ray crystallography using Cu Kα radiation. The mixed-biogenetic skeleton could be derived from the hypothetical precursors related to coumarin and dihydrobotrydiol, and the latter may be derived from the coisolated 10-oxodehydrodihydrobotrydial (2) or a similar analogue.
Two new chromone glucosides, named cnidimosides A and B, were isolated from whole plants of Cnidium japonicum. Their structures were determined to be 5,7-dihydroxy-6-[(2Z)-3-β-d-glucopyranosylmethyl-2-butenyl]-2-methyl-4H-[1] benzopyran-4-one and 5-hydroxy-7-methoxy-6-[(2Z)-3-β-d-glucopyranosylmethyl-2-butenyl]-2-methyl-4H-[1] benzopyran-4-one, respectively.
Concise synthesis of NADH: ubiquinone oxidoreductase (complex I) antagonist pterulinic acid (1a) is reported. The key architectural framework in the natural product, 1-benzoxepine ring skeleton, was smoothly prepared from known salicylaldehyde 2g and phosphorane 3 via tandem SN2/Wittig reaction. Pterulinic acid was prepared in 5 steps from 2g with overall yield of 25%. The versatility of tandem SN2/Wittig reaction was investigated. This tandem reaction tolerated various alkyl, ether, tertiaryamine and nitro substituted salicylaldehyde, and it gave the corresponding 1-benzoxepine ring skeleton in moderated yield (21–72%).
Seven new chromone glycosides, monnierisides A (3), B (10), C (11), D (12), E (13), F (15) and G (16) were isolated from Cnidium. monnieri, together with ten known chromone derivatives, undulatoside A (1), cnidimol C (2), saikochromoside A (4), cnidimoside A (5), cnidimoside B (6), 2-methyl-5-hydroxy-6-(2-butenyl-3-hydroxymethyl)-7-(β-d-glucopyranosyloxy)-4H-1-benzopyran-4-one (7), cnidimol D (8), hydroxycnidimoside A (9), umtatin (14) and 6'-hydroxylangelicain (17). The structures of isolated compounds were determined on the basis of spectroscopic analysis including 1D, 2D NMR and HR-MS. Among the compounds isolated, compounds 5, 6, 9 and 10 significantly inhibited adipocyte differentiation as measured by fat accumulation in 3T3-L1 cells using Oil Red O staining.
This review deals with some bioorganic chemical aspects of isoflavonoids. Its highlights are rather restricted to the structural modifications and the diverse oxygenated side attachments originating from the isoprenoid substituents, 3,3-dimethylallyl (prenyl), 1,1-dimethylallyl and geranyl groups. Some aspects of naturally occurring isoflavonoids, their new classes and biological functions are also described.
Chemical investigations on the ethanolic extract of the dried fructus of Cnidium monnieri offered three chromones and eight coumarins. Among them, a new chromone and a new coumarin were identified and elucidated as 5,7-dihydroxy-6-[(2Z)-4-(β-d-glucopyranosyl)oxy-3- methylbut-2-enyl]-2-hydroxymethyl-4H-1-benzopyran-4-one (1, hydroxycnidimoside A) and (rel 1'S,2'R)-8-(2,3-epoxy-1-hydroxy-3-methylbutyl)-7-methoxycoumarin (8, hydroxyosthole epoxide), respectively, by extensive analyses of spectroscopic data including 1- and 2-D NMR, MS, UV, OR, IR, and HRMS data. The other known compounds were identified by analyses of spectroscopic data and by comparison with literature reported.
The structures of two novel fungal antibiotics, isolated from a Pterula species, that interfere with the NADH:ubiquinone oxidoreductase and inhibit the respiration of eucaryotes, were determined by spectroscopic techniques. Both compounds, pterulinic acid (1a) and pterulone (2), contain a 1-benzoxepin ring system and are chlorinated. Pterulinic acid (1a), which was obtained as a 1:5 inseparable mixture of the two isomers (Z)-1a and (E)-1a, in addition contains a furan. Their structures were determined by mass spectrometry and NMR spectroscopy, and 2D heteronuclear correlation experiments permitted the assignment of all NMR signals.
Two novel biscoumarins, cnidimonal (1) and cnidimarin (2), and two new coumarin derivatives, 5-formylxanthotoxol (3) and 2'-deoxymeranzin hydrate (4), were isolated from a traditional Chinese crude drug, the fruits of Cnidium monnieri, together with 15 known compounds. Among the known compounds, five of the minor compounds were isolated for the first time from this plant. The structures of 1-4 were determined with the use of spectroscopic methods.
Bupleuri radix, an important crude drug in the prescriptions of Chinese traditional medicine, was found to contain small amounts of previously unrecorded constituents, three saikogenins (1, 2 and 3), two polyhydroxysterols (4 and 5), one trihydroxy fatty acid (6a), one lignan (7a), and one simple new chromone, designated saikochromone A (8). These results represent a more complex profile of the chemical constituents of Bupleuri Radix, than was previously known.
Extraction of the timber of sneezewood has given a number of chromones and coumarins. The constitution of two novel chromones, karenin and desoxykarenin, has been elucidated by conversion to a derivative of a third chromone peucenin.
Aus Rinde, Holz und Blättern von C. pulverulentum werden die Cneorum-Chromone C bis H mit den Strukturen 7a, 3a, 7d, 9a, 3c und 5 und Cneorum-Cumarin B (10b) isoliert. Synthesen der Chromone 2b, 3b und eine Partial-Synthese für 7d aus 7a werden beschrieben.
Extractives from Cneoraceae, IV Chromones and Coumarins from Cneorum pulverulentum
From the bark, wood and leaves of C. pulverulentum, the Cneorum-chromones C–H (formulae 7a, 3a, 7d, 9a, 3c, and 5 respectively), and Cneorum-coumarin B (formula 10 b) have been isolated. Syntheses of the chromones 2b, 3b and a partial synthesis of 7d from 7a are described.