Isolation and characterization of miscellaneous terpenoids of Schisandra chinensis

Two new bisnortriterpenoids with 18-norschiartane skeleton, wuweizidilactones G (1) and H (2), four new highly oxygenated nortriterpenoids based on a schisanartane skeleton, schindilactones D-G (3-6), a pre-schisanartane skeleton, pre-schisanartanin B (7), and a novel 3,4-seco-21,26-olide-artane triterpenoid wuweizilactone acid (8), along with 24 known terpenoids with different carbon frameworks, have been isolated from the acetone extract of the stems and leaves of Schisandra chinensis. The terpenoids produced by this plant have chemical diversity. The structures of new compounds 1-8 have been characterized by spectroscopic data interpretation. The cytotoxicity and anti-HIV-1 activity of all the Schisandra nortriterpenoids were evaluated.     

Discovery of novel sesquiterpenoids from a gorgonian Menella sp.

A novel sesquiterpenoid, menelloide A (1), which was found to possess a new carbon skeleton, and a new guaiane-type sesquiterpenoid, menelloide B (2), along with (+)-chloranthalactone B (3), an enantiomer of the known sesquiterpenoid, chloranthalactone B (4), were isolated from a gorgonian coral identified as Menella sp. The structures of sesquiterpenoids 1-3 were established by spectroscopic methods and by comparison of the data with those of related metabolites. Sesquiterpenoids 1 and 3 displayed inhibitory effects on the generation of superoxide anion by human neutrophils.     

Briaexcavatins A and B, novel briaranes from the octocoral Briareum excavatum

Two novel briaranoidal derivatives, designated as briaexcavatins A (1) and B (2), along with two known metabolites, excavatolides B and C (3 and 4), were isolated from the octocoral Briareum excavatum. Both compounds 1 and 2 possess unprecedented 5,6-epoxy moiety in the 10-membered ring. Diterpenoid 1 possesses a novel pentacyclic skeleton with a ε-lactone. The structures of diterpenoids 1 and 2 were elucidated by interpretation of spectral data and the absolute stereochemistry was established by application of modified Mosher’s method on 3.     

Schilancidilactones A and B: two novel tetranortriterpenoids with an unprecedented skeleton from Schisandra lancifolia

Schilancidilactones A (1) and B (2), two novel tetranortriterpenoids possessing an unprecedented skeleton, have been isolated from the stems of Schisandra lancifolia. Their structures were elucidated on the basis of extensive spectroscopic analysis. The relative configurations of 1 were further determined by single-crystal X-ray crystallography. Compounds 1 and 2 were tested for their cytotoxicity against four tumor cell lines NB4, A549, SH-SY5Y, and PC-3, and compound 1 was further tested for its anti-HIV-1 activity.     

Novel alkaloids, paxdaphnines A and B with unprecedented skeletons from the seeds of Daphniphyllum paxianum

Two novel Daphniphyllum alkaloids with unprecedented skeletons, namely paxdaphnines A (1) and B (2), have been isolated from the seeds of Daphniphyllum paxianum. Paxdaphnine A (1) is a 19-nor-Daphniphyllum alkaloid with highly caged skeleton, and paxdaphnine B (2) is the first 1,19-bisnor-Daphniphyllum alkaloid. The relative structures of 1 and 2 were elucidated by spectral methods, and their unique biosynthetic pathway postulated. The absolute structure of 1 was determined by X-ray diffraction of the iodide derivative (1a) of 1, and the absolute stereochemistry of 2 was proposed by correlation with the biosynthetic pathway for 1.     

Three novel nortriterpenoids from Notochaete hamosa Benth. (Labiatae)

Three nortriterpenoids, notohamosin A (1), B (2) and C (3) with novel skeleton, and eight known compounds were isolated from the ethanol extract of the whole plants of Notochaete hamosa Benth. (Labiatae). On the basis of spectral evidence including 1D, 2D NMR, IR and MS data, their structures were elucidated. The relative configurations of compounds 1, 2 and 3 were determined according to NOESY experiments.     

Rumphellclovane A, a novel clovane-related sesquiterpenoid from the gorgonian coral Rumphella antipathies

A novel clovane-related derivative, rumphellclovane A (1), which was found to possess a new carbon skeleton, and a new natural clovane, 2β-hydroxyclovan-9-one (2), were isolated from the gorgonian coral Rumphella antipathies. The structures of metabolites 1 and 2 were elucidated by spectroscopic analysis and by comparison of the spectral data with those of related clovane analogues. A plausible biosynthetic pathway of 1 was proposed.     

Penicillones A and B, two novel polyketides with tricyclo [5.3.1.0] undecane skeleton, from a marine-derived fungus Penicillium terrestre

Two novel polyketides, penicillones A (1) and B (2), with tricyclo [5.3.1.0^3,8] undecane skeleton, were isolated from Penicillium terrestre. Their structures and relative stereochemistries were determined on the basis of spectroscopic methods. The absolute configuration of 2 was established by the modified Mosher’s method, while that of 1 was deduced from the similar CD absorptions of 1 and 2. Compound 1 showed weak cytotoxicities against P338 and A-549 cell lines, while 2 was inactive against P388.     

Tubiferal A, a backbone-rearranged triterpenoid lactone isolated from the myxomycete Tubifera dimorphotheca, possessing reversal of drug resistance activity

Tubiferal A, a novel rearranged triterpenoid lactone, has been isolated from field-collected fruit bodies of the myxomycete, Tubifera dimorphotheca, and its structure elucidated by spectral data. Tubiferal A (1) possesses a 9,10-secocycloartan-16,21-olide skeleton, and this new compound exhibited a reversal effect of vincristine (VCR) resistance (more than 4-fold) against VCR-resistant KB cell lines. Tubiferal B (2), corresponding to the seco acid of 1 was also isolated, but showed no comparable activity.     

Two novel polycyclic spiro lignans from Gymnotheca involucrata

Two novel lignans, gymnothespirolignans A (1) and B (2), possessing a rare polycyclic spiro skeleton, were isolated from the endemic plant of Gymnotheca involucrata Pei. Their structures were determined by spectroscopic evidences and the absolute configurations were confirmed by single crystal X-ray diffraction analysis. Compounds 1 and 2 showed promising antiviral activities against RSV with an IC₅₀ value of 31.87 and 17.51 μM, respectively.     

Excavatoids A-D, new polyoxygenated briaranes from the octocoral Briareum excavatum

Three polyoxygenated briaranes, including two new compounds, excavatoids A (1) and B (2), and a known metabolite, briaexcavatin I (3), were isolated from the cultured octocoral Briareum excavatum. Moreover, the wild type B. excavatum, collected off southern Taiwan coast, yielded two new 5,6-epoxybriaranes, excavatoids C (4) and D (5). The structures of new compounds 1, 2, 4, and 5 were determined by spectroscopic methods and the structure of 1 was further confirmed by X-ray diffraction data analysis. The X-ray structure for briaexcavatin I (3) was also reported for the first time. Excavatoid A (1) is the first briarane which possesses six hydroxy groups and a 17-methoxy group. Excavatoid C (4) is the first 12,13-secobriarane which possesses a novel pentacyclic skeleton with an ?-lactone. Excavatoid D (5) displayed moderate inhibitory effects on superoxide anion generation and elastase release by human neutrophils.     

Cyclooxygenase-2 enzyme inhibitory withanolides from Withania somnifera leaves

Four novel withanolide glycosides and a withanolide have been isolated from the leaves of Withania somnifera. The structures of the novel compounds were elucidated as physagulin D (1→6)-β-d-glucopyranosyl-(1→4)-β-d-glucopyranoside (1), 27-O-β-d-glucopyranosyl physagulin D (2), 27-O-β-d-glucopyranosyl viscosalactone B (3), 4,16-dihydroxy-5β, 6β-epoxyphysagulin D (4), and 4-(1-hydroxy-2,2-dimethylcyclo-propanone)-2,3-dihydrowithaferin A (5) on the basis of 1D-, 2D NMR and MS spectral data. In addition, seven known withanolides withaferin A (6), 2,3-dihydrowithaferin A (7), viscosalactone B (8), 27-desoxy-24,25-dihydrowithaferin A (9), sitoindoside IX (10), physagulin D (11), and withanoside IV (12) were isolated. These withanolides were assayed to determine their ability to inhibit cycloxygenase-1 (COX-1) and cyclooxygenase-2 (COX-2) enzymes and lipid peroxidation. The withanolides tested, except compound 9, showed selective COX-2 enzyme inhibition ranging from 9 to 40% at 100 μg/ml. Compounds 4, 10 and 11 also inhibited lipid peroxidation by 40, 44 and 55%, respectively. The inhibition of COX-2 enzyme by withanolides is reported here for the first time.     

Penilactones A and B, two novel polyketides from Antarctic deep-sea derived fungus Penicillium crustosum PRB-2

Two highly oxygenated polyketides, penilactones A and B (1 and 2), containing a new carbon skeleton formed from two 3,5-dimethyl-2,4-diol-acetophenone units and a γ-butyrolactone moiety, together with five known compounds (3-7) were isolated from an Antarctic deep-sea derived fungus Penicillium crustosum PRB-2. Penilactones A and B possess antipodal absolute stereochemistries. Their structures were elucidated by spectroscopic methods, and their absolute configurations were assigned by single-crystal X-ray diffraction and CD analyses. A plausible biogenetic pathway for 1-2 is proposed.     

Feroniellins A-C, novel cytotoxic furanocoumarins with highly oxygenated C10 moieties from Feroniella lucida

Three new furanocoumarins, named feroniellins A (1), B (2), and C (3), were isolated from the roots of Feroniella lucida. Compounds 1-3 are novel structures having an oxolane, oxane, and oxepane moiety. Their overall structures and configurations were determined by spectral and chemical methods. The cytotoxicities of 1-3 were evaluated against human KB and HeLa carcinoma cells.     

Two new biscembranes with unprecedented carbon skeleton and their probable biogenetic precursor from the Hainan soft coral Sarcophyton latum

A new cembranolide diterpene, isosarcophytonolide D (1), and two biscembranes with an unprecedented fused carbon skeleton, bislatumlides A (3) and B (4), were isolated from the Hainan soft coral Sarcophyton latum. Their structures and relative stereochemistry were established by 1D and 2D NMR spectroscopic techniques. Compounds 3 and 4 should be obtained by Diels-Alder addition of two cembranoid units. Compound 1 could be one of the biosynthetic precursors. Both 3 and 4 showed mild cytotoxicity toward A549, HT-29, and P388 cell lines.     

Alkaloids and citrinins from marine-derived fungus Nigrospora oryzae SCSGAF 0111

A new pyrrolidinone, nigrospine (1), a new indole alkaloid, nigrospin A (2) and two new citrinins, nigrospins B and C (3-4) were isolated from a culture broth of the marine-derived fungal strain Nigrospora oryzae SCSGAF 0111. Their structures were determined by spectroscopic analysis, and the absolute configurations of 1 and 2 were determined by the Mosher ester technique. Compound 1 contains a rare 2,3-dihydro-benzofuran[2,3-c]2-pyrrolidone skeleton.     

New xenicane diterpenoids from Xenia florida

Three new xenicane diterpenoids, designated xeniolactones A (1), B (2), and C (3), were isolated from Xenia florida collected in Taiwan. Compound 1 possesses a novel structure having a heterotricyclic skeleton in cyclononane system. The structures of 1-3 were elucidated on the basis of extensive spectroscopic analysis. The cytotoxicity of 1-3 was also evaluated against human cancer cell lines.     

Two novel diterpenoids from Isodon rubescens var. lushanensis

Two novel diterpenoids, luanchunins A (1) and B (2), along with their precursor, kamebakaurin (3), had been isolated from the stems and leaves of Isodon rubescens var. lushanensis. Their structures were elucidated on the basis of extensive spectroscopic analyses. Compounds 1 and 2 showed potent cytotoxic activity against HL-60 with IC₅₀ values of 4.81 μM and 3.52 μM, respectively. Plausible pathways for the biosynthesis of 1 and 2 were also postulated.     

Two novel 3,4-seco-trinorlanostane triterpenoids isolated from Ganoderma fornicatum

Two novel 3,4-seco-25,26,27-trinorlanostane triterpeniod compounds, fornicatins A and B (1 and 2) have been isolated from the fruiting body of G. fornicatum. The structural elucidation of 1 and 2 were accomplished by extensive NMR analysis. The relative stereochemistry of 2 was established by single crystal X-ray crystallography, which also confirmed the novel carbon skeleton of the new triterpenoid. An ether linkage of C-4 with C-7 in 1 is unprecedented in natural triterpenoids. Both compounds were tested for their inhibitory effects on rabbit platelet aggregation induced by PAF, ADP, or AA.     

Mekongenines A and B, two new alkaloids from Bousigonia mekongensis

Mekongenine A (1) possessing an unprecedented structure constituted from the union of a rare 2,7-seco eburnamine half and an aspidospermine alkaloid, together with a new bisindole alkaloid, mekongenine B (2), consisting of an eburnamine-aspidospermine type skeleton, was isolated from Bousigonia mekongensis. Their structures were elucidated by means of spectroscopic methods and those of 2 were further confirmed by X-ray diffraction. The absolute configurations of 1 and 2 were determined by comparison of quantum chemical TDDFT calculated and experimental ECD spectra. Mekongenines A (1) and B (2) exhibited cell growth inhibitory activities against various human cancer cell lines.