Diarylheptanoids from Curcuma comosa

Three new diarylheptanoids, designated 1-(3,4-dihydroxyphenyl)-7-(4-hydroxyphenyl)-(6E)-6-hepten-3-ol (1), 1-(3-hydroxyphenyl)-7-(3,4-dihydroxyphenyl)-3-methoxy-(6E)-6-heptene (2), (3R, 5R)-1-(3,4-dihydroxyphenyl)-7-phenyl-heptane-3,5-diol (3) and three known compounds, were isolated from rhizomes of Curcuma comosa. Structures of the compounds were determined by spectroscopic data analysis.     

Triterpenoid saponins from Anemone raddeana

Three new triterpenoid saponins, named raddeanoside R₂₀ (1), raddeanoside R₂₁ (2) and raddeanoside R₂₂ (3), were isolated from the water soluble part of Anemone raddeana. The chemical structures of these new compounds were elucidated by chemical and spectroscopic methods.     

Chemical constituents from the leaves of Cinnamomum parthenoxylon (Jack) Meisn. (Lauraceae)

Phytochemical investigation of the ethanolic extract from the leaves of Cinnamomum parthenoxylon (Jack) Meisn. led to the isolation of (3R, 4R, 3′R, 4′R)-6,6′-dimethoxy-3, 4, 3′, 4′-tetrahydro-2H, 2′H-[3, 3′]bichromenyl-4, 4′-diol (1), 4-hydroxybenzaldehyde (2), 1,2,4-trihydroxybenzene (3), kaempferol-3-O-α-l-rhamnoside (4), herbacetin (5), quercetin-3-O-α-l-rhamnoside (6), daucosterol (7), and β-sitosterol (8). The structures were established by extensive analysis of their MS and NMR spectroscopic data and comparison with literature data. In the present research, all of the isolated compounds 1–8 are reported for the first time in the species C. parthenoxylon. Compounds 1–6 were firstly isolated from genus Cinnamomum. Compounds 1, 3, 5 and 6 have not been reported from any species in Lauraceae family. The chemotaxonomic significance of the isolated compounds is discussed.     

Trinorsesquiterpenoids from Inula racemosa

Four trinorsesquiterpenoids (1–4) were isolated from the roots of Inula racemosa and the structures of two new compounds, (4R,5S,10S)-5-hydroxy-11,12,13-trinoreudesm-6-en-8-one (1) and (4R,5R,10R)-4,15-epoxy-11,12,13-trinoreudesman-8-one (3), were elucidated by extensive spectroscopic analysis. Furthermore, the structure of compound 2a should be revised as (4R,5R,10S)-5-hydroxy-11,12,13-trinoreudesm-6-en-8-one (2) and compound 2 showed antiproliferative activity against A549, HepG2, and HT1080 cell lines with IC50 values of 3.71, 5.94, and 3.95 μg/mL, respectively.     

New flavonoids from the fruits of Cornus mas,Cornaceae

One new β-hydroxychalcone, 4-acetoxy-5,2′,4′,6′,β-pentahydroxy-3-methoxychalcone (1), one new flavanone, 7,3′-dihydroxy-5,4′-dimethoxyflavanone (2) and seven known compounds, 2R, 3R-trans-aromadendrin (3), naringenin-7-O-methylether (4), myricetin (5), quercetin-3-O-rutinoside (6), ursolic acid (7), gallic acid (8) and d-glucose (9) were isolated from the methanolic fruit extract of Cornus mas L. (=Cornus mascula L.), Cornaceae. The structures of the new compounds were elucidated on the basis of extensive spectroscopic methods, including 2D NMR experiments and of known compounds by comparison of physical and spectral data with literature.     

Three new jacaranone derivatives from the aerial parts of Senecio chrysanoides DC. with their cytotoxic activity

Three new jacaranone derivatives, namely, (1R)-ethyl 1-hydroxy-4-oxo-2-cyclohexenylacetate (1), (1R, 6S)-ethyl 6-ethoxy-1-hydroxy-4-oxo-2-cyclohexenylacetate (2) and (1R, 6R)-ethyl 6-ethoxy-1-hydroxy-4-oxo-2-cyclohexenylacetate (3), along with a known jacaranone derivative, ethyl 1-hydroxy-4-oxocyclohexylacetate (4) were isolated from the aerial parts of Senecio chrysanoides DC.. Their structures were elucidated by spectroscopic methods, optical rotation calculations and CD analyses. All the isolated compounds were evaluated for their cytotoxicity against three human cancer cell lines in vitro. Compound 2 exhibited moderate inhibitory effects against these cancer cell lines.     

Antiproliferative constituents from Aphananthe aspera leaves

Extensive screening for the antiproliferative activity of different compounds found in trees was performed by extracting the leaves of Aphananthe aspera (Thunb.) Planch and then using chromatographic separation to afford 2 new compounds, (2S,4R)-2-carboxy-4-(E)-p-caffeoyl-1-methyl-hydroxyproline (1) and 5-O-caffeoyl quinic acid-(7′R,8′S,7′′E)-3′,4′,3′′-dihydroxy-4′′,7′-epoxy-8′,5′′-neolign-7′-ene-9- carboxyl (2). In addition, 6 known compounds were discovered from the leaves of this plant. The structural determination of all compounds, including their absolute configurations, was established by UV, IR, HRESIMS, 1D and 2D NMR, and CD spectroscopy. The novel compound 1 showed strong antiproliferative activity against human breast adenocarcinoma cells MCF-7 and MDA-MB-231.     

Sulfur-containing constituents and one 1H-pyrrole-2-carboxylic acid derivative from pineapple [Ananas comosus (L.) Merr.] fruit

Two sulfur-containing compounds, (S)-2-amino-5-((R)-1-carboxy-2-((E)-3-(4-hydroxy-3-methoxyphenyl)allylthio)ethyl-amino)-5-oxopentanoic acid (1) and (S)-2-amino-5-((R)-1-(carboxymethylamino)-3-((E)-3-(4-hydroxyphenyl)allylthio)-1-oxopropan-2-ylamino)-5-oxopentanoic acid (2), and one 1H-pyrrole-2-carboxylic acid derivative, 6-(3-(1H-pyrrole-2-carbonyloxy)-2-hydroxypropoxy)-3,4,5-trihydroxy-tetrahydro-2H-pyran-2-carboxylic acid (3), together with eighteen known phenolic compounds, were isolated from the fruits of pineapple. Their structures were elucidated by a combination of spectroscopic analyses. Some of these compounds showed inhibitory activities against tyrosinase. The half maximal inhibitory concentration values of compounds 1, 4, 5, 6, 7 are lower than 1 mM. These compounds may contribute to the well-known anti-browning effect of pineapple juice and be potential skin whitening agents in cosmetic applications.     

Minor phenolics from Angelica keiskei and their proliferative effects on Hep3B cells

A new coumarin, (?)-cis-(3′R,4′R)-4′-O-angeloylkhellactone-3′-O-β-d-glucopyranoside (1) and two new chalcones, 3′-[(2E)-5-carboxy-3-methyl-2-pentenyl]-4,2′,4′-trihydroxychalcone (4) and (±)-4,2′,4′-trihydroxy-3′-{2-hydroxy-2-[tetrahydro-2-methyl-5-(1-methylethenyl)-2-furanyl]ethyl}chalcone (5) were isolated from the aerial parts of Angelica keiskei (Umbelliferae), together with six known compounds: (R)-O-isobutyroyllomatin (2), 3′-O-methylvaginol (3), (?)-jejuchalcone F (6), isoliquiritigenin (7), davidigenin (8), and (±)-liquiritigenin (9). The structures of the new compounds were determined by interpretation of their spectroscopic data including 1D and 2D NMR data. All known compounds (2, 3, and 6–9) were isolated as constituents of A. keiskei for the first time. To identify novel hepatocyte proliferation inducer for liver regeneration, 1–9 were evaluated for their cell proliferative effects using a Hep3B human hepatoma cell line. All isolates exhibited cell proliferative effects compared to untreated control (DMSO). Cytoprotective effects against oxidative stress induced by glucose oxidase were also examined on Hep3B cells and mouse fibroblast NIH3T3 cells and all compounds showed significant dose-dependent protection against oxidative stress.     

Evaluation of andrographolide-based analogs derived from Andrographis paniculata against Mythimna separata Walker and Tetranychus cinnabarinus Boisduval

To discover new natural-product-based pesticides, we structurally modified andrographolide, a labdane diterpenoid isolated from Andrographis paniculata, and stereoselectively prepared a series of 12α-(substituted)benzylamino-14-deoxyandrographolide derivatives (I–V). Three-dimensional structures of compounds 3c, 3d, IIIa and IIIb were further determined by single-crystal X-ray diffraction. Compounds IIa (R¹ = n-C₃H₇, R² = PhCH₂) exhibited more promising insecticidal activity against Mythimna separata than toosendanin. Compounds 3a (R¹ = H), Ib (R¹ = H, R² = 4-ClPhCH₂), and IVa (R¹ = 4-ClPh, R² = PhCH₂) showed potent acaricidal activity against Tetranychus cinnabarinus.     

A new bicyclic sesquiterpene from the marine sponge associated fungus Emericellopsis minima

A new sesquiterpene (5E)-2-methyl-5-[(1′R*, 5′R*)-2-methylidene-7-oxobicyclo[3.2.1]oct-6-ylidene]-4-oxopentanoic acid (1) was isolated, in addition to the dihydroisocoumarin cis-(3R, 4R)-4-hydroxymellein, ergosterol peroxide and helvolic acid, from the culture of the fungus Emericellopsis minima associated with the marine sponge Hyrtios erecta. The structures of all the compounds were elucidated using spectroscopic data from 1D, 2D NMR and HRESITOFMS. Compounds 1 and cis-(3R, 4R)-4-hydroxymellein were found to show neither antimicrobial nor the in vitro growth inhibitory activities on three human tumor cell lines.     

Sesquiterpenoids and lignans from the fruits of Illicium simonsii Maxim

Twenty-two known compounds were isolated from the 95% alcohol extract of the fruits of Illicium simonsii Maxim, including seven sesquiterpenoids (16–22) and fifteen lignans (1–15). In the present research, compounds 3 ((7S,8R,8′S)-3,3′-dimethoxy-4,4′,9-trihydroxy-7,9′-epoxylignan-7′-one), 4 ((−)-(7′S,8S,8′R)-4,4′-dihydroxy-3,3′,5,5′-tetramethoxy-7′,9-epoxylignan-9′-ol-7-one), 5 ((+)-8-hydroxypinoresinol), 6 ((+)-8-hydroxymedioresinol), 8 ((2R,3R)-2β-(4″-hydroxy-3″-methoxybenzyl)-3α-(4′-hydroxy-3′-methoxybenzyl)-γ-butyrolactone 2-O-(β-D-glucopyranoside), 12 ((+)-8-methoxyisolariciresinol), 13 (α-conidendrin), 14 (boehmenan) and 15 (7R,8R,7′E-7′,8′-didehydro-4,7,9,9′- tetrahydroxy-3-methoxy-8-O-4′-neolignan) were reported from the Illicium genus for the first time, and compounds 1 (simulanol), 7 ((+)-secoisolariciresinol monoglucoside), 10 ((+)-9-O-β-D-glucopyranosyl lyoniresinol), 11 ((+)-isolariciresinol), 18 (neoanisatin), 19 (veranisatin A), 20 (4,5-d₂-8′-oxo-dihydrophaseic acid) and 22 (Oligandrumin A) were firstly isolated from the plant. Their structures were elucidated on the basis of NMR spectroscopic and mass spectrometric data. Moreover, the chemotaxonomic significance of the isolated compounds is discussed.     

Tyrosinase inhibitory activity of three new glycosides from Breynia fruticosa

Two new flavanone glycoside derivatives and one new sulfur-containing spiroacetal glycoside, (2R, 3R)-3-acetyl-7-methoxy-(−)-epicatechin 5-O-(6-isobutanoyl)-β-d-glucopyranoside (1), (2R, 3R)-3-acetyl-7-methoxy-(−)-epicatechin 5-O-[6-(2-methylbutanoyl)]-β-d-glucopyranoside (2) and 4-[(carboxymethyl)thio]-5′-hydroxy-phyllaemblic acid O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside ester (3), along with twelve known flavonoids and one known sulfur-containing spiroacetal glycoside, were isolated from Breynia fruticosa. Their structures were elucidated by the use of extensive spectroscopic methods (UV, IR, HR-ESI-MS, 1D and 2D NMR, and CD). The in vitro inhibition of tyrosinase activity by all of these compounds was also evaluated, and we concluded that the flavanol-containing 5-O- and 7-O-sugar moieties possessed more potent effects than the other compounds examined herein.     

Phenolic derivatives and an antifungal and cytototoxic labdane diterpenoid from the root bark of Turraeanthus mannii

The structures of two new compounds from the root bark of Turraeanthus mannii (Meliaceae) were determined as (3R,4R,3′R,4′R)-6,6′-dimethoxy-3,4,3′,4′-tetrahydro-2H,2′H-[3,3′]bichromenyl-4,4′-diol (1) and 15-acetoxy-labda-8(17),12E,14Z-trien-16-al (2) by means of spectroscopic analysis. Five further known compounds including one coumarin derivative, one chromenone, two labdane diterpenes and one pregnane steroid have been isolated from the same source. In antifungal and cytotoxic assays, 15-acetoxy-labda-8(17),12E,14Z-trien-16-al (2) was highly active against Mucor miehei and Artemia salina, respectively.     

A constituent of Alpinia katsumadai suppresses allergic airway inflammation

Two new compounds, named as (3R)-5,7-dihydroxy-3-isopropyl-3-methylisochroman-1-one (1), and (1R,3R,4S)-1-(4′-methyl-phenyl)-3,4-dihydro-3,4-dimethyl-1H-2-benzopyran-5,6,8-triol (2), were isolated from seeds of Alpinia katsumadai Hayata. Structures of compounds 1 and 2 were elucidated and determined on the basis of spectroscopic analysis. Additionally, compound 1 significantly suppressed allergic airway inflammation induced by OVA through reducing airway hyperresponsiveness. Moreover, the inflammation suppression was associated with a marked decrease in the Th2 cytokines and IgE production.     

Two new nonacosanetriols from Ginkgo biloba sarcotesta

Two new fatty alcohols named as (7S,8R,11S)-nonacosanetriol (1) and (10R,12R,15S)-nonacosanetriol (2), along with eight known compounds including ginkgolic acid (3), hydroginkgolic acid (4), sciadopitysin (5), ginkgetin (6), isoginkgetin (7), ginkgolide A (8), ginkgolide B (9) and ginkgolide C (10) have been isolated from the petroleum ether extract of Ginkgo biloba sarcotesta. Their structures were elucidated by means of chemical and extensive spectroscopic analysis. The absolute stereochemistry of compounds 1 and 2 was elucidated on the spectroscopic analysis of the R- and S-MTPA esters. Compounds 1 and 2 exhibited slight activity of antithrombin and moderate activity of antiplatelet aggregation in vitro. This was the first report regarding the anticoagulative activities of biflavonoids in G. biloba, and isoginkgetin (7) showed significant antithrombin and antiplatelet aggregation activity.     

N-Acetyldopamine derivatives from Periostracum Cicadae

Five new N-acetyldopamine (NADA) derivatives (1–5) and one known NADA quinone methide (6) were isolated from Periostracum Cicadae (the cast-off shell of the cicada Cryptotympana pustulata Fabricius), which is known as chantui in China and is used in traditional Chinese medicine to treat soreness of the throat, hoarseness, itching, and spasms. By combined analysis of one-dimensional and two-dimensional nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, CD spectra, and chemical evidence, the structures of the isolated compounds were established as (R)-N-(2-(3,4-dihydroxyphenyl)-1-ethoxy-2-oxoethyl)acetamide (1), (1R,2R)-N-(1,2-diethoxy-2-(3,4-dihydroxyphenyl)-ethyl)acetamide (2), (R)-N-(1-acetamido-2-ethoxy-2-(3,4-dihydroxyphenyl)-ethyl)acetamide (3), (1R,2R)-N-(2-(3,4-dihydroxyphenyl)-2-ethoxy-1-methoxyethyl)acetamide (4), (1S,2S)-N-(2-(3,4-dihydroxyphenyl)-2-ethoxy-1-methoxyethyl)acetamide (5), and (R)-N-(2-(3,4-dihydroxyphenyl)-2-methoxyethyl)acetamide (6).     

Chemical constituents from the root bark of Dictamnus dasycarpus Turcz. (Rutaceae) and their chemotaxonomic significance

This work described the isolation and characterization of seven compounds from Dictamnus dasycarpus Turcz., including one new ester, (2R)-4-(2,2-dimethyl-5-oxotetrahydrofuran-3-yl)-2-hydroxypent-3-anoic acid ethyl ester (1); and six known glycosides (2–7). The structure of compound 1 was elucidated on the basis of extensive spectral analyses, including IR, HR-ESIMS, 1D and 2D NMR (NOESY, HMBC and HSQC). All these compounds were described here for the first time from the genus Dictamnus. Moreover, the results provide further information about the diversity of compounds in the genus Dictamnus.     

A pair of new sesquiterpene isomers containing spiro heterocyclic skeleton from plant-derived fungus Botryosphaeria dothidea

A pair of new sesquiterpene isomers containing a spiro heterocyclic skeleton, dothimes A (1) and B (2), together with six known compounds, quindoline (3), (S)-3-(3-indolyl)lactic acid methyl ester (4), dankasterone B (5), dibutyl phthalate (6), (1S,3R,4R,7S)-3,4-dihydroxy-α-bisabolol (7), and p-hydroxybenzaldehyde (8), were isolated from the plant-derived fungus Botryosphaeria dothidea. The structures of all isolated compounds were determined based on extensive spectroscopic analyses, including 1D/2D nuclear magnetic resonance (NMR), and high resolution electrospray ionization mass spectrometry (HRESIMS) data, as well as by comparison with literature reports. Compounds 1 and 2 exhibited inhibitory effects on lipopolysaccharide (LPS)-induced nitric oxide (NO) production with IC₅₀ values of 63.66 and 58.29 μM, respectively.