Three New Atisane Diterpenoids from Spiraea japonica

Three new atisane diterpenoids, spiratisanins A – C ( 1  –  3 , resp.), featuring a phenylacryloxyl substituted ent‐atisane skeleton, were isolated from Spiraea japonica together with two known atisine diterpene alkaloids, spiramine A ( 4 ) and spiradine F ( 5 ). The structures of these new compounds were elucidated as (5β,7α,8α,9β,10α,12α,16β)‐16‐hydroxyatisan‐7‐yl (2E)‐3‐phenylprop‐2‐enoate ( 1 ), (5β,7α,8α,9β,10α,12α,16α)‐16‐hydroxyatisan‐7‐yl (2E)‐3‐phenylprop‐2‐enoate ( 2 ), and (5β,8α,9β,10α,12α,16β)‐16‐hydroxyatisan‐20‐yl (2E)‐3‐phenylprop‐2‐enoate ( 3 ) on the basis of spectroscopic analysis.     

New ent‐Pimarane Diterpenes from the Roots of Aralia dumetorum

Four new ent‐pimarane diterpenes were isolated from the EtOH extract of Aralia dumetorum, together with three known compounds involving ent‐pimar‐8(14),15‐dien‐19‐oic acid ( 5 ), ent‐pimar‐8(14),15‐dien‐19‐ol ( 6 ), and ent‐kaur‐16‐en‐19‐oic acid ( 7 ). By detailed analyses of the MS, IR, and NMR data, the structures of four new diterpenes were characterized as (5β,9β,10α,13α)‐pimara‐6,8(14),15‐trien‐18‐oic acid ( 1 ), (5β,7β,9β,10α,13α)‐7‐methoxypimara‐8(14),15‐dien‐18‐oic acid ( 2 ), (5β,9β,10α,13α,14β)‐14‐methoxypimara‐7,15‐dien‐18‐oic acid ( 3 ), and (5β,10α,13α,14α)‐14‐hydroxypimara‐7,9(11),15‐trien‐18‐oic acid ( 4 ). The cytotoxic activities of compounds 1  –  7 were assayed in vitro through MTT method.     

Three New Derivatives and Others Constituents from the Roots and Twigs of Trilepisium madagascariense DC

Three new compounds, trilepisflavene ( 1 ), trilepisdepsidone ( 2 ), and daturadiol stearate ( 3 ), together with nine known compounds, 2‐hydroxy‐4‐[(4‐hydroxy‐2‐methoxy‐6‐methylbenzoyl)oxy]‐6‐methylbenzoic acid ( 4 ), lichexanthone ( 5 ), naringenin ( 6 ), 3′,4′,5,7‐tetrahydroxyflavanone ( 7 ), 2‐hydroxybenzoic acid ( 8 ), methyl 2,4‐dihydroxy‐6‐methylbenzoate ( 9 ), β‐amyrin ( 10 ), eurothridiol palmitate ( 11 ), and β‐sitosterol ( 12 ), were isolated from the AcOEt extract of the twigs and the roots of Trilepisium madagascariense. Acetylation of eurothridiol palmitate was carried out and a new acetylated derivative ( 13 ) was obtained. The structures of the isolated and acetylated compounds were elucidated on the basis of spectroscopic analysis. Antimicrobial activity of all these compounds was evaluated using Mueller–Hinton broth (MHB) and Mueller–Hinton agar (MHA) method. Trilepisdepsidone , 2‐hydroxy‐4‐[(4‐hydroxy‐2‐methoxy‐6‐methylbenzoyl)oxy]‐6‐methylbenzoic acid, 3′,4′,5,7‐tetrahydroxyflavanone, and naringenin exhibited moderate to weak antimicrobial activity.     

Diterpenoids from the Wood of Cunninghamia konishii

Investigation of the wood of Cunninghamia konishii resulted in the isolation and characterization of one new abietane diterpenoid, (6α,7β)‐7,8‐epoxy‐6‐hydroxyabieta‐9(11),13‐dien‐12‐one ( 1 ), and two new labdane diterpenoids, (12R)‐12‐hydroxylabda‐8(17),13(16),14‐trien‐19‐oic acid ( 2 ) and (12R)‐12‐hydroxylabda‐8(17),13(16),14‐trien‐18‐oic acid ( 3 ). The structures of these new compounds were elucidated by analysis of their spectroscopic data.     

Three New Cassane‐Type Diterpenes from Caesalpinia minax

Three new cassane‐type diterpenes, 14‐dehydroxy‐12,16‐dihydrocaesaldekarin L ( 1 ), 1‐deacetyl‐12‐ethoxyneocaesalpin N ( 2 ), and 1‐deacetylneocaesalpin N ( 3 ), together with two known cassane‐type diterpenes, neocaesalpin A and neocaesalpin L, were isolated from the EtOH extract of the twigs and leaves of Caesalpinia minax. Their structures were elucidated by spectroscopic methods, as well as by comparison of their spectral data with those of related compounds.     

New Cytotoxic Myrsinane‐Type Diterpenes from Euphorbia prolifera

Four new myrsinol diterpenes, proliferins A–D ( 1 – 4 , resp.) were isolated from the EtOH extracts of the roots of Euphorbia prolifera, along with four known compounds, euphorprolitherin B ( 5 ), euphorprolitherin D ( 6 ), SPr5 ( 7 ), and 14‐desoxo‐3‐O‐propionyl‐5,15‐di‐O‐acetyl‐7‐O‐nicotinoylmyrsinol‐14β‐acetate ( 8 ). Their structures were established on the basis of spectroscopic methods, including HR‐ESI‐MS, and 1D‐ and 2D‐NMR techniques. The cytotoxicity of compounds 1, 3 , and 4 against cancer cells was evaluated, with compound 1 being active against A2780 cancer cells.     

(+)‐N‐Formylnorglaucine Rotamers from Unonopsis stipitata Diels

(+)‐N‐formylnorglaucine ( 1 ), an aporphine alkaloid containing a formyl group linked to the heterocyclic nitrogen, was isolated from the leaves of Unonopsis stipitata, an Amazon medicinal plant. The chemical structure was characterized based on 1D‐ and 2D‐NMR spectroscopy and HR‐ESI‐MS. NMR spectra revealed that 1 is composed of two rotamers ( 1a and 1b ) in a ratio of approximately 2:1. In addition, the fragmentation behavior of 1 displayed an unusual fragmentation pattern compared to regular aporphine alkaloids. Thus, this compound is reported for the first time as a natural product in this study.     

Three New ent‐Kaurane Diterpenoids from Siegesbeckia pubescens

Three new ent‐kaurane glucopyranosides, 2‐O‐[β‐D ‐apiofuranosyl‐(1→3)‐2‐O‐isovaleryl‐β‐D ‐glucopyranosyl]‐4‐epi‐atractyligenin ( 1 ), 2‐O‐[β‐D ‐apiofuranosyl‐(1→3)‐2‐O‐isovaleryl‐β‐D ‐glucopyranosyl]atractyligenin ( 2 ), and 2‐O‐[β‐D ‐apiofuranosyl‐(1→3)‐2‐O‐(3‐methylpentanoyl)‐β‐D ‐glucopyranosyl]‐4‐epi‐atractyligenin ( 3 ), along with 2‐O‐(2‐O‐isovaleryl‐β‐D ‐glucopyranosyl)‐4‐epi‐atractyligenin ( 4 ), were isolated for the first time from the aerial parts of Siegesbeckia pubescens. The structures were established by extensive spectroscopic analyses including 1D ‐ and 2D ‐NMR (HSQC, HMBC, and ROESY), and HR‐ESI‐MS, and by comparison with published data.     

Five New Oleanane Triterpenoid Saponins from the Aerial Parts of Elsholtzia bodinieri

Five new oleanane triterpenoid saponins, bodiniosides H – L ( 1  –  5 , resp.), were isolated from the aerial parts of Elsholtzia bodinieri. Their structures were elucidated on the basis of spectroscopic techniques, including HSQC, HMBC, and HSQC‐TOCSY experiments, together with acid hydrolysis and GC analysis.     

Three New Pregnane Alkaloids from Pachysandra terminalis

Three new pregnane alkaloids, pachystermine C ( 1 ), pachysanamine A ( 2 ), and pachysanamine B ( 3 ), together with four known ones, pachystermine B ( 4 ), pachysamine A ( 5 ), (20S)‐20‐(dimethylamino)‐16α‐hydroxy‐3β‐(3′α‐isopropyl)lactam‐5α‐pregnan‐4‐one ( 6 ), and E‐salignone ( 7 ), were isolated from Pachysandra terminalis. The chemical structures of the new alkaloids were elucidated by spectroscopic methods. All the compounds were evaluated for their inhibitory activities against HL‐60, SMMC‐7721, A‐549, MCF‐7, and SW480 cell lines, some of the compounds showed stronger cytotoxicity for the test cell lines, especially compounds 2 , 3 , and 7 .     

Three New Lycopodium Alkaloids from Phlegmariurus fargesii

Three new Lycopodium alkaloids, fargesiines A – C ( 1  –  3 , resp.), along with a known compound ( 4 ), were isolated from the whole plants of Phlegmariurus fargesii. Their structures were elucidated on the basis of spectroscopic data and chemical correlations. Compounds 1  –  4 were tested in an assay for acetylcholinesterase (AChE) inhibitory activity.     

Two New Nimbolinin‐Type Limonoids from the Fruits of Melia toosendan

Two new nimbolinin‐type limonoids, 12‐ethoxynimbolinins E and F ( 1 and 2 , resp.), together with seven known analogues, 1α‐benzoyloxy‐3α‐acetoxyl‐7α‐hydroxy‐12β‐ethoxynimbolinin ( 3 ), nimbolinin B ( 4 ), meliatoosenin L ( 5 ), 14,15‐deoxy‐11‐oxohavanensin 3,12‐diacetate ( 6 ), 12α‐hydroxymeliatoosenin ( 7 ), toosendansin A ( 8 ), and toosendansin C ( 9 ), were isolated from the fruits of Melia toosendan. The structures of these compounds were elucidated by spectroscopic analysis. All the compounds were evaluated for their cytotoxicity against five tumor cell lines.     

Three New Chalcones from the Aerial Parts of Angelica keiskei

Three new chalcones, 3′‐carboxymethyl‐4,2′‐dihydroxy‐4′‐methoxychalcone ( 1 ), (±)‐4,2′,4′‐trihydroxy‐3′‐[(3‐hydroxy‐2,2‐dimethyl‐6‐methylenecyclohexyl)methyl]chalcone ( 2 ), and 2′′‐hydroxyangelichalcone ( 3 ), were isolated from the aerial parts of Angelica keiskei (Umbelliferae) together with five known compounds, artocarmitin A ( 4 ), (+)‐cis‐(3′R,4′R)‐methylkhellactone ( 5 ), (?)‐trans‐(3′R,4′S)‐methylkhellactone ( 6 ), 3,4‐dihydroxanthotoxin ( 7 ), and (Z)‐p‐coumaryl alcohol ( 8 ). The known compounds 4  –  8 were identified from A. keiskei for the first time. The structures of 1  –  3 were elucidated by interpreting spectroscopic data including 1D‐ and 2D‐NMR.     

Megastigmane Glycosides from Docynia indica and Their Anti‐inflammatory Activities

Using various chromatographic methods, three new megastigmane glycosides, docynicasides A – C ( 1  –  3 ) and ten known, (6S,9R)‐vomifoliol 9‐O‐β‐d ‐xylopyranosyl‐(1′′→6′)‐O‐β‐d ‐glucopyranoside ( 4 ), hyperin ( 5 ), quercitrin ( 6 ), quercetin 3‐α‐l ‐arabinofuranoside ( 7 ), naringenin 7‐O‐β‐d ‐glucopyranoside ( 8 ), phloridzin ( 9 ), phloretin 2′‐O‐β‐d ‐xylopyranosyl‐(1→6)‐β‐d ‐glucopyranoside ( 10 ), pinosylvin 3‐O‐β‐d ‐glucopyranoside ( 11 ), tormentic acid ( 12 ), and chlorogenic acid methyl ester ( 13 ) were isolated from the fruits of Docynia indica. Their chemical structures were elucidated by physical and chemical methods. All the isolated compounds were evaluated for the inhibitory activity on NO production in LPS‐stimulated BV2 cells. As the results, compounds 3  –  5 showed significant inhibitory activity on LPS‐stimulated NO production in BV2 cells with the IC₅₀ values ranging from 21.0 to 29.3 μm .     

Anti‐Inflammatory Activity of a Novel Acetylene Isolated from the Roots of Angelica tenuissima Nakai

Three polyacetylenes, one novel and two known, were isolated from the root of Angelica tenuissima. Using ¹H‐ and ¹³C‐NMR, COSY, HMBC, and HMQC, their structures were found to be (3R,8S)‐heptadeca‐1‐en‐4,6‐diyne‐3,8‐diol ( 1 ), falcarindiol ( 2 ), and oplopandiol ( 3 ). Absolute configurations of compound 1 were established using Mosher's esterification. In addition, the polyacetylenes ( 1 – 3 ) were evaluated for their anti‐inflammatory activity. Compounds 1 and 3 showed potent inhibitory activity against lipopolysaccharide‐induced nitric oxide (NO) production in RAW267.7 macrophage cells with IC₅₀ values of 4.31 and 5.06 μm, respectively. Compound 1 strongly inhibited inducible nitric oxide synthase (iNOS) and cyclooxygenase (COX)‐2 in a concentration‐dependent manner.     

Caesaljaponins A and B: New Cassane‐Type Furanoditerpenoids from the Seeds of Caesalpinia decapetala var. japonica

Two new cassane‐type furanoditerpenoids, designated caesaljaponin A and caesaljaponin B ( 1 and 2 , resp.), were isolated from seeds of Caesalpinia decapetala var. japonica. The structures were elucidated by spectroscopic data, and the absolute configuration of 1 was determined by X‐ray crystallographic analysis using the anomalous scattering of CuK_α radiation.     

New Labdane‐Type Diterpenoids from Amentotaxus argotaenia

A new labdane diterpene, amentotaxin A ( 1 ), and an unprecedented dinorlabdane diterpene, amentotaxin B ( 2 ), were isolated from the stems of Amentotaxus argotaenia (Hance) Pilger , together with seven known compounds. Their structures were identified by in‐depth spectroscopic and mass‐spectrometric analyses.     

A New Seco-Abietanoid from the Bark of Cryptomeria japonica

Chemistry of Natural Compounds - A new seco-abietanoid, 12-hydroxy-6,7-seco-abieta-8,11,13-triene-6,7-dioic acid (1), was isolated from the methanol extract of the bark of Cryptomeria japonica. The...     

New Eunicellin Diterpenes and 9,10‐Secosteroids from the Gorgonian Muricella sibogae

Bioactivity‐guided isolation of the rare gorgonian Muricella sibogae (Nutting ) yielded the two new eunicellin diterpenes sibogin A and B ( 1 and 2 ), the three new 9,10‐secosteroids sibogol A–C ( 6 – 8 ), together with the three known eunicellin diterpenes 3 – 5 and the five known 9,10‐secosteroids 9 – 13 . Their structures were established by extensive spectral analysis (1D‐ and 2D‐NMR, IR, and MS). The cytotoxicity of the isolates 1 – 13 was evaluated in vitro against the selected tumor cell lines P388 and BEL‐7402. All the compounds showed only weak activity against P388 cell lines, with an inhibition rate ranging from 10 to 60% at a concentration of 50 μg/ml, whereas the were inactive against BEL‐7402 cell lines.