Seco-prezizaane-type sesquiterpenes and an abietane-type diterpene from Illicium minwanense

A methanol extract of the pericarps of Illicium minwanense afforded seven new seco-prezizaane-type sesquiterpenes (2-8) and a new abietane-type diterpene (9), together with six previously known compounds (1 and 10-14). The structures of the new compounds, (1S)- and (1R)-minwanenone (2 and 3), 1alpha-hydroxy-6-deoxypseudoanisatin (4), (2S)-hydroxy-6-deoxypseudoanisatin (5), 3-oxopseudoanisatin (6), (3S,6R)-4,7-epoxy-6-deoxypseudoanisatin (7), 7-O-methylpseudomajucin (8), and (+)-8,11,13,15-abietatetraene (9), were elucidated by spectroscopic data analysis and chemical transformations. The absolute configurations of 1 and 5 were established by X-ray crystallographic analysis of their p-bromobenzoyl derivatives.     

Phenolic constituents of the roots of Sophora flavescens

From the roots of Sophora flavescens collected in Taiwan, four new prenylflavonoids, sophoraflavanone K (1), sophoraflavanone L (2), 8-lavandulylkaempferol (3), and cyclokuraridin (4), a new arylbenzofuran, 2-(2,4-dihydroxy-5-prenylphenyl)-5,6-methylenedioxybenzofuran (5), and a new prenyldibenzoyl derivative, sophoradione (6), were isolated. The structures of 1-6 were determined by spectroscopic data analysis. Compounds 2-6 were evaluated for cytotoxic activity against the KB epidermoid carcinoma cell line.     

Antioxidant principles from Bauhinia tarapotensis

A new cyclohexenone (1) and a new caffeoyl ester derivative (2), together with the known compounds (-)-isolariciresinol 3-alpha-O-beta-D-glucopyranoside (3), (+)-1-hydroxypinoresinol 1-O-beta-D-glucopyranoside (4), isoacteoside (5), luteolin 4'-O-beta-D-glucopyranoside (6), and indole-3-carboxylic acid (7), were isolated from the leaves of Bauhinia tarapotensis. The structures of these new compounds were determined by spectroscopic data analysis. The antioxidant activities of 1-7 were determined by measuring their free radical scavenging effects, using the 1,1-diphenyl-2-dipicrylhydrazyl free radical (DPPH) and Trolox equivalent antioxidant activity (TEAC) methods, and the coupled oxidation of beta-carotene and linoleic acid. Compounds 3-5 showed good activities in the DPPH and TEAC tests, while compounds 1 and 2 were active in the coupled oxidation of beta-carotene and linoleic acid bioassay.     

Africane-type sesquiterpenoids from the Argentine liverwort Porella swartziana and their antibacterial activity

Seven africanes (1, 2a,b, 3-6), two of them new (1, 2a), three secoafricanes (7-9), one of them new (7), and two norsecoafricanes (10, 11a), one of them new (10), all of them swartzianin-type, have been isolated from an Argentine collection of the endemic liverwort Porella swartziana. The structures of the new compounds were established by extensive 1D and 2D NMR spectroscopic data. Absolute configurations of compounds 2a, 2b, and 10 were derived on the basis of CD spectra. The compounds were tested for activity against a variety of microbes, but none were found to exhibit significant antibacterial activity.     

Bacopaside III,bacopasaponin G,and bacopasides A,B, and C from Bacopa monniera

Two new saponins, 3-O-[6-O-sulfonyl-beta-d-glucopyranosyl-(1-->3)]-alpha-l-arabinopyranosyl pseudojujubogenin (1) and 3-O-[alpha-l-arabinofuranosyl-(1-->2)]-alpha-l-arabinopyranosyl jujubogenin (2), a new matsutaka alcohol derivative, (3R)-1-octan-3-yl-(6-O-sulfonyl)-beta-d-glucopyranoside (3), a new phenylethanoid glycoside, 3,4-dihydroxyphenylethyl alcohol (2-O-feruloyl)-beta-d-glucopyranoside (4), and a new glycoside, phenylethyl alcohol [5-O-p-hydroxybenzoyl-beta-d-apiofuranosyl-(1-->2)]-beta-d-glucopyranoside (5), were isolated from Bacopa monniera. Their structures were established by NMR, MS, and chemical methods.     

Homo- and nor-plakotenin, new carboxylic acids from the Palauan sponge Plakortis lita.

A specimen of Plakortis lita from Palau yielded the new carboxylic acids, homo-plakotenin (2a), the sodium salt of homo-plakotenin (2b), the sodium salt of nor-plakotenin (3), the sodium salt of plakotenin (1b), and the known compound plakotenin (1a). The structures of the new acids were elucidated by interpretation of spectral data and by comparison with the known compound. Compounds 1a, 1b, and 2a were found to significantly reduce proliferation of rheumatoid synovial fibroblasts.     

Antimalarial β-carboline and indolactam alkaloids from Marinactinospora thermotolerans, a deep sea isolate

Four new β-carboline alkaloids, designated marinacarbolines A-D (1-4), two new indolactam alkaloids, 13-N-demethyl-methylpendolmycin (5) and methylpendolmycin-14-O-α-glucoside (6), and the three known compounds 1-acetyl-β-carboline (7), methylpendolmycin (8), and pendolmycin (9) were obtained from the fermentation broth of Marinactinospora thermotolerans SCSIO 00652, a new actinomycete belonging to the family Nocardiopsaceae. Their structures were elucidated by extensive MS and 1D and 2D NMR spectroscopic data analyses. The structure of compound 1 was further confirmed by single-crystal X-ray crystallography. The new compounds 1-6 were inactive against a panel of eight tumor cell lines (IC50>50 μM) but exhibited antiplasmodial activities against Plasmodium falciparum lines 3D7 and Dd2, with IC50 values ranging from 1.92 to 36.03 μM.     

Diterpenes, sesquiterpenes, and a C15-acetogenin from the marine red alga Laurencia mariannensis

In addition to 10 known compounds (7- 16), one new brominated diterpene, 10-hydroxykahukuene B (1), two new sesquiterpenes, 9-deoxyelatol (2) and isodactyloxene A (3), one new brominated C 15-acetogenin, laurenmariallene (4), and two new naturally occurring halogenated sesquiterpenes (5 and 6) that were previously obtained as intermediates in a biomimetic synthetic study of rhodolaureol and rhodolauradiol have been isolated and identified from the organic extract of the marine red alga Laurencia mariannensis. The structures of these compounds were established by spectroscopic methods. The antibacterial and antifungal activities of new compounds 1-4 were evaluated.     

Constituents from the leaves of Phellodendron amurense var. wilsonii and their bioactivity

Two new dihydroflavonols, phellodensin-A (1) and phellodensin-C (2); three new coumarins, phellodenol-A (3), phellodenol-B (4), and phellodenol-C (5); one new chlorophyll, phellophyll-a (6); and one new phenyllactate, (2R)-sodium 3-phenyllactate (7), in addition to 35 known compounds have been isolated from the leaves of Phellodendron amurense var. wilsonii. The structures of the new compounds were established based on 1D, 2D NMR and mass spectral analyses. The stereochemistry at the C-2, C-3, and C-2' ' positions of new dihydroflavonol 1 was determined by CD spectroscopy. The known compounds were identified by comparison with authentic samples. The antioxidant and antityrosinase activities were also described.     

Diterpenoids from the flowers of Rhododendron molle

Five new grayanane-type diterpenoids, rhodomolleins IX (1), X (2), XI (3), XII (4), and XIII (5), a new kalmane-type diterpenoid, rhodomollein XIV (6), and seven known diterpenoids, grayanotoxin II, rhodomolleins I and XIX, rhodojaponins II, III, and VI (7), and kalmanol, were isolated from the flowers of Rhododendron molle. The structures of 1-6 were elucidated by spectroscopic methods, including 1D and 2D NMR experiments.     

Cytotoxic and anti-inflammatory triterpenoids from Toona ciliata

Toonaciliatavarins A-H (1-8), including three new protolimonoids (1-3), two new tirucallane-type triterpenoids (4 and 5), and three new tetranortriterpenoids (6-8), and 10 known compounds were isolated from the stem barks of Toona ciliata Roem. var. henryi. Their structures were identified on the basis of spectroscopic analysis. The absolute configurations of 2 and 8 were determined by ECD calculation. The new isolates were evaluated for their cytotoxicities using six human cancer cell lines and also for their inhibitory effects on lipopolysaccharide-induced nitric oxide production in RAW264.7 cells. Compounds 4 and 5 showed moderate cytotoxicities, and the protolimonoids (1-3) exhibited marked inhibitory effects on LPS-stimulated NO production.     

Sesqui- and diterpenoids from the Japanese liverwort Jungermannia infusca.

Seven new cuparane-type (1-7), one new acorane-type (8), one new monocyclic-type (9), and one new prelacinane-type (10) sesquiterpenoid as well as two new clerodane-type (11, 12) and one new halimane-type (13) diterpenoid were isolated from the Japanese liverwort Jungermannia infusca, together with 12 known cuparane- (14-21) and aromadendrane-type (22) sesquiterpenoids and labdane- (23) and ent-kaurane-type (24) diterpenoids. The structures for 1-13 were determined using extensive NMR techniques and by chemical degradation and X-ray crystallographic analysis.     

Unusual isomeric corniculatolides from mangrove, Aegiceras corniculatum

Four new isomeric macrolides of combretastatin D-2 congeners named isocorniculatolide A (1), 11-O-methylisocorniculatolide A (2), 11-O-methylcorniculatolide A (3), and 12-hydroxy-11-O-methylcorniculatolide A (4), and the known corniculatolide A (5), arjunolic acid, and maslinic acid were isolated from the CHCl(3) extract of the bark of Aegiceras corniculatum. The structures of the new compounds (1-4) were elucidated by a combination of spectroscopic analysis (1-5), chemical modifications, and single-crystal X-ray analysis (1).     

Phloroglucinols with antioxidant activity and xanthonolignoids from the heartwood of Hypericum geminiflorum

A new phloroglucinol, hyperielliptone HA (1/1a), a new spirophloroglucinol possessing an unprecedented skeleton, hyperielliptone HB (2/2a), and two new xanthonolignoids, hyperielliptones HC (3) and HD (4), were isolated from the heartwood of Hypericum geminiflorum. Compounds 1/1a and 2/2a were obtained as tautomeric pairs. The structures and relative configurations of these compounds were elucidated by spectroscopic methods. In biological testing, compound 2/ 2a revealed significant inhibition of oxidative DNA damage and an inhibitory effect on xanthine oxidase.     

Alkaloids from Gelsemium elegans

Three new alkaloids, gelsebanine (1), 14alpha-hydroxyelegansamine (2), and 14alpha-hydroxygelsamydine (3), and a new extraction artifact , gelsebamine (4), together with 12 known alkaloids, were isolated from the stems and leaves of Gelsemium elegans. The structures of 1-4 were determined by spectroscopic methods, especially 2D NMR techniques. Compounds 1-4 were evaluated for cytotoxic activity against four tumor cell lines, and gelsebamine (4) selectively inhibited the A-549 human lung adenocarcinoma cell line.     

Cytotoxic germacranolides and acyclic diterpenoides from the seeds of Carpesium triste

Four new highly oxygenated germacranolides (1, 4, 6, and 7) and four new acyclic diterpenes (8-11), along with three known germacranolides (2, 3, and 5), were isolated from the seeds of Carpesium triste. The structures of the new compounds were elucidated by spectroscopic methods including IR, HRESIMS, and 1D and 2D NMR experiments, and the absolute configurations of compounds 1 and 8-10 were established by CD and Mosher's methods, respectively. Compounds 1, 2, and 4-10 were evaluated for their in vitro cytotoxic activity against cultured SMMC-7721 (human hepatoma), HL-60 (human promyelocytic leukemia), and L02 (human hepatocyte) cell lines. Compounds 1, 2, and 4-7 exhibited significant cytotoxicity against HL-60 cells, and compound 10 exhibited cytotoxicity against SMMC-7721 cells.     

Triterpenoids from Schisandra lancifolia with anti-HIV-1 activity

A new trinorcycloartane triterpenoid, lancifodilactone H (1), and a new A ring-secocycloartane triterpenoid, lancifoic acid A (2), together with a known compound, nigranoic acid (3), were isolated from the leaves and stems of Schisandra lancifolia. Their structures were elucidated by spectroscopic data analysis. Compound 1 features a biosynthetically modified seven-membered lactone ring, which was confirmed by single-crystal X-ray diffraction. Compounds 1-3 exhibited weak anti-HIV-1 activity in vitro.     

Cytotoxic flavaglines and bisamides from Aglaia edulis

Two new cyclopenta[b]benzofurans, aglaroxin A 1-O-acetate (2) and 3'-methoxyaglaroxin A 1-O-acetate (3), a new benzo[b]oxepine, 19,20-dehydroedulisone A (4), and five new cyclopenta[bc]benzopyrans, edulirin A (5), edulirin A 10-O-acetate (6), 19,20-dehydroedulirin A (7), isoedulirin A (8), and edulirin B (9), were isolated from the bark of Aglaia edulis, along with one known cyclopenta[b]benzofuran, aglaroxin A (1). Additionally, four new amides, aglamides A-D (10-13), as well as three known compounds, aglalactone, scopoletin, and 5-hydroxy-3,6,7,4'-tetramethoxyflavone, were isolated from the leaves and/or twigs of this species. The structures of the new compounds (2-13) were elucidated by interpretation of their spectroscopic data. All isolates obtained in this study were evaluated for cytotoxicity against both several human cancer cell lines (Lu1, LNCaP, and MCF-7) and a nontumorigenic (HUVEC) cell line. Among these isolates, the cyclopenta[b]benzofurans (1-3) exhibited potent in vitro cytotoxic activity (ED50 range 0.001 to 0.8 microg/mL). Aglaroxin A 1-O-acetate (2) was further evaluated in the in vivo P388 lymphocytic leukemia model, by intraperitoneal injection, but found to be inactive in this model.     

Two Alangium alkaloids from Alangium lamarckii

Two new Alangium alkaloids, 1',2'-dehydrotubulosine (1) and alangine (2), were isolated from the dried fruits of Alangium lamarckii along with tubulosine (3), isotubulosine (4), deoxytubulosine, cephaeline, isocephaeline, psychotrine, neocephaeline, 10-O-demethylcephaeline, 2'-N-(1"-deoxy-1" -beta-D-fructopyranosyl)cephaeline, protoemetine, protoemetinol, salsoline, and alangiside. The structures of the new alkaloids (1 and 2) were determined by spectroscopic and chemical means.     

Benzophenones and biflavonoids from Rheedia edulis

Two new polyisoprenylated benzophenones, 32-hydroxy-ent-guttiferone M (1) and 6-epi-guttiferone J (2), along with seven known compounds, 6-epi-clusianone (3), guttiferone A (4), xanthochymol (5), guttiferone E (6), isoxanthochymol (7), (+)-volkensiflavone (8), and (+)-morelloflavone (9), were identified from the seeds and rinds of Rheedia edulis. Compounds 1-3 and 5-9 have been isolated and identified from this species for the first time. The structures of the new compounds were elucidated mainly by analysis of their 1D and 2D NMR spectroscopic data, and their absolute configurations were determined by comparison of their experimental optical rotation and electronic circular dichroism measurements with those values predicted by DFT calculations. Compound 1 showed significant antioxidant activity in both DPPH and ABTS free radical scavenging assays, whereas compound 2 was inactive.