Calyciphylline G, a novel alkaloid with an unprecedented fused-hexacyclic skeleton from Daphniphyllum calycinum

Calyciphylline G (1), a novel Daphniphyllum alkaloid with an unprecedented fused-hexacyclic skeleton containing a 5-azatricyclo[6.2.1.0^1,5]undecane ring, has been isolated from the stem of Daphniphyllum calycinum (Daphniphyllaceae), and the structure and relative stereochemistry were elucidated on the basis of spectroscopic data.     

Lycopladine H, a novel alkaloid with fused-tetracyclic skeleton from Lycopodium complanatum

A novel Lycopodium alkaloid, lycopladine H (1), with a fused-tetracyclic ring system consisting of an azocane ring connected to a [2,2,2]-bicyclooctane ring and a 3-piperidone ring, was isolated from the club moss Lycopodium complanatum. The structure and relative stereochemistry of 1 were elucidated on the basis of spectroscopic data.     

Cochinchistemonine, a novel skeleton alkaloid from Stemona cochinchinensis

Cochinchistemonine (1), an alkaloid with a novel skeleton, was isolated from the roots of Stemona cochinchinensis collected from northern Vietnam. Its structure was established on the basis of one- and two-dimensional NMR and other spectroscopic studies. The relative configuration was confirmed by single crystal X-ray diffraction experiment.     

Daphnilongerine, an unprecedented fused pentacyclic ring system alkaloid from Daphniphyllum longeracemosum Rosenth.

An unusual yuzurine-type alkaloid daphnilongerine (1), with an unprecedented fused pentacyclic skeleton in addition to seven known ones, daphnigracine (2), daphnezomine R, daphnigraciline, yuzurine, longistylumphyllines A, daphnilongeranin C, and calycinine A, was isolated from the fruits of Daphniphyllum longeracemosum. The structure and relative stereochemistry of 1 were determined by spectroscopic analysis.     

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.     

Vilmoraconitine, a novel skeleton C19-diterpenoid alkaloid from Aconitum vilmorinianum

A novel C₁₉-diterpenoid alkaloid vilmoraconitine (1) was isolated from the roots of Aconitun vilmorinianum. Its structure was mainly determined by MS, 2D NMR, and X-ray methods. This is the first aconitine-type C₁₉-diterpenoid alkaloid with one three-membered ring at C-8, C-9, and C-10.     

Naupliolide, a sesquiterpene lactone with a novel tetracyclic skeleton from Nauplius graveolens subsp. odorus

The aerial parts of Nauplius graveolens subsp. odorus (Schousb) Wikl. afforded a novel sesquiterpene lactone (1) named naupliolide together with the known 6,7,9,10-tetradehydroasteriscanolide 2 and asteriscunolides A-D 3a-d. The structure of compound 1 corresponds to a novel skeleton of 14,15-dimethyl-7,13-dioxotricyclic[6.4.0.0^9,11]dodeca-12,13-olide, and was established on the basis of spectroscopic methods including 2D-NMR. The coexistence of naupliolide 1 together with the structurally related sesquiterpene lactones asterisculolides A-D (3a-d) and 6,7,9,10-tetradehydroasteriscanolide 2, seems to indicate their biosynthetic relationship.     

Hericirine,a novel anti-inflammatory alkaloid from Hericium erinaceum

A novel ergosterol conjunction-type alkaloid, hericirine (1), was isolated from the dried fruiting bodies of Hericium erinaceum. The overall framework of 1 was isolated, and combined with hericerin and ergosterol. Its structure was elucidated based on spectroscopic analysis using 1D and 2D NMR, IR and HRESIMS techniques. We found that hericirine significantly inhibited protein expression of iNOS and COX-2 and reduced NO, PGE₂, TNF-α, IL-6 and IL-1β production in RAW264.7 cells exposed to LPS.     

Gomerones A-C, halogenated sesquiterpenoids with a novel carbon skeleton from Laurencia majuscula

The structures and relative sterochemistry of three halogenated sesquiterpenoids gomerones A-C, 1-3, isolated from Laurencia majuscula are described. They are representative of a novel carbon skeleton, gomerane, biogenetically derived from cyclization of a β-chamigrene precursor. A biogenetic relationship with related sesquiterpenoids from lower terrestrial plants Hepaticae of genera Bazzania, Mannia, Mylia, and Rebouli as well as higher plants of genera Cupressus and Juniperus has been established.     

A trypanocidal diterpene with novel skeleton from Dracocephalum komarovi

A new diterpene, komarovispirone (1) with a spiro-octahydroindene skeleton, was isolated from Dracocephalum komarovi. The structure was elucidated by extensive analyses of spectral data. Komarovispirone (1) showed trypanocidal activity against epimastigote of Trypanosoma cruzi, the causative agent of American trypanosomiasis, with a minimum lethal concentration of 23 μM.     

Ancisheynine, a novel naphthylisoquinolinium alkaloid from Ancistrocladus heyneanus

A novel naphthylisoquinoline alkaloid, ancisheynine 1, was isolated from the aerial part of Ancistrocladus heyneanus Wallich ex J. Graham (Ancistrocladaceae). Ancisheynine 1 contained a previously undescribed N-2,C-8′-linkage between the isoquinoline and naphthalene units and its structure was established by spectroscopic methods.     

Daphniglaucin C, a novel tetracyclic alkaloid from Daphniphyllum glaucescens

A novel Daphniphyllum alkaloid with an unprecedented tetracyclic ring system consisting of an octahydroindole and a hexahydroazulene rings, daphniglaucin C (1), has been isolated from the leaves of Daphniphyllum glaucescens and the structure and relative stereochemistry were elucidated on the basis of spectroscopic data. Daphniglaucin C (1) inhibited the polymerization of tubulin.     

Hupermine A,a novel C16N2-type Lycopodium alkaloid from Huperzia phlegmaria

A novel C₁₆N₂-type Lycopodium alkaloid consisting of a quinolizidine with a 6-dimethylaminohexyl side chain, hupermine A (1), was isolated from the club moss of Huperzia phlegmaria, and the structure and relative stereochemistry were elucidated on the basis of spectroscopic data.     

N-Demethyl-sauroxine,a novel Lycodine Group alkaloid from Huperzia saururus

The present study describes the isolation and identification of N-demethyl-sauroxine, a novel Lycopodium alkaloid obtained from Huperzia saururus (Lam.) Trevis. (Lycopodiaceae). Its structure and relative stereochemistry were elucidated on the basis of its spectral data and chemical correlations. Additionally, acetylcholinesterase inhibitory activity was evaluated (IC₅₀ = 209.6 ± 1.1 μM). The structure of the already identified alkaloid sauroxine was also re-validated through two dimensional NMR data.     

Chloctanspirones A and B, novel chlorinated polyketides with an unprecedented skeleton, from marine sediment derived fungus Penicillium terrestre

Two novel chlorinated sorbicillinoids named chloctanspirones A (1) and B (2), possessing an unprecedented bicyclo[2.2.2]octane-2-spiro cyclohexane skeleton, together with their quasi-precursors terrestrols K (3) and L (4), two additional new chlorinated compounds, were isolated from a marine sediment derived fungus Penicillium terrestre. Their structures including absolute stereochemistries were elucidated by analysis of NMR, MS data, and TDDFT CD calculations. The cytotoxic effects of 1-4 were preliminarily evaluated in HL-60 and A-549 cells. Compound 1 was active against both HL-60 and A-549 cells with IC₅₀s 9.2 and 39.7 μM, respectively, while 2 showed weaker activity only against HL-60 cells (IC₅₀ 37.8 μM).     

Agariblazeispirols A and B, an unprecedented skeleton from the cultured mycelia of the fungus, Agaricus blazei

Agariblazeispirols A and B, which have a unique steroidal skeleton, have been isolated from the cultured mycelia of Agaricus blazei (Agaricaceae). The absolute structure of Agariblazeispirol A was established to be (20S,22R,23R,24S)-13β,22:22,25-diepoxy-5-methoxy-14β-methyl-18-nor-des-A-ergosta-5,7,9,11-tetraen-23-ol by extensive 1D and 2D NMR spectral data, and X-ray analysis. The structure of Agariblazeispirol B was elucidated to be a stereoisomer of agariblazeispirol A at its carbon 22, (20S,22S,23R,24S)-13β,22:22,25-diepoxy-5-methoxy-14β-methyl-18-nor-des-A-ergosta-5,7,9,11-tetraen-23-ol by comparison of extensive 1D and 2D NMR spectral data with those of agariblazeispirol A. Both compounds showed a moderate circumvention of drug resistance on mouse leukemia P388/VCR cells.     

Calycilactone A, a novel hexacyclic alkaloid from Daphniphyllum calycillum

A novel Daphniphyllum alkaloid with a rearranged fused-hexacyclic ring system, calycilactone A, was isolated from the leaves of Daphniphyllum calycillum (Daphniphyllaceae), and the structure and relative stereochemistry of the new compound were elucidated on the basis of spectroscopic data.     

Synthetic approaches towards an indole alkaloid isolated from the marine sponge Halichondria melanodocia

The exocyclic analogue of the indole alkaloid isolated from the marine sponge Halichondria melanodocia has been prepared via olefination of a phosphonoester derived from 3-(2-bromoacyl)indole. The formation of an unexpected indolylazepine is also discussed.     

Oldhamine A, a novel alkaloid from Daphniphyllum oldhami

Oldhamine A, a novel alkaloid with an unusual cyclopentadienyl anion in the fused-pentacyclic skeleton was isolated from the twigs of Daphniphyllum oldhami. The structure of oldhamine A was elucidated based on the spectroscopic data and the single-crystal X-ray diffraction crystallography. It is the first X-ray diffraction of the Daphniphyllum alkaloids with nitrogen-containing two pentacyclic rings. The inter-conversion between cyclopentadienyl anion and conjugated enolic unit was also conducted.     

Leucolusine, a tetracyclic alkaloid with a novel ring system incorporating an oxindole moiety and fused piperidine-tetrahydrofuran rings

A tetracyclic ring-opened oxindole alkaloid, possessing an unprecedented ring system incorporating fused piperidine-tetrahydrofuran rings, has been isolated from the Malayan species, Leuconotis griffithii. The structure was established by analysis of the spectroscopic data and a possible biogenetic pathway from an Aspidosperma precursor is presented.