Chemical Constituents of the Aerial Part of Celastrus Hypoleucus

Fourteen compounds including eight triterpenoids, 12‐oleanaen‐3β‐ol (β‐amyrin) ( 1 ), 12‐oleanaen‐3β‐caffeate ( 2 ), 9(11),12‐oleanadien‐3β‐ol ( 3 ), 9(11),12‐oleanadien‐3‐one ( 4 ), 9(11),12‐oleanadien‐3 β‐caffeate ( 5 ), friedela‐3‐one (friedelin) ( 6 ), friedela‐3‐one‐29‐ol ( 7 ), and 12‐gammateraen‐3 β‐ol (tetrehymanol) ( 8 ); one steroid, β‐sitosterol ( 9 ); one long‐chain acid, octadecadienoic acid ( 10 ); two esters, ester of n‐octaolecyl‐4‐hydroxy‐cinnamate ( 11 ), and ester of n‐octadecyl‐caffeic acid ( 12 ); one diterpene, 8β,19‐dihydroxy‐3‐oxopimar‐15‐ene ( 13 ); one sesquiterpene, 1β,2β,9α‐trihydroxy‐β‐dihydroagarofuran ( 14 ) were isolated from the aerial part of Celastrus hypoleucus. These compounds were characterized and identified by physical and spectral methods. All compounds were isolated for the first time from this plant. Among them 12‐oleanaen‐3β‐caffeate ( 2 ) and 9(11),12‐oleanadien‐3β‐caffeate ( 5 ) are two new compounds, and ester of n‐octadecyl‐caffeic acid (12) possessed antilipoperoxidative effect by specifically scavenging the hydroxyl free radical (?OH) in vitro.     

Identification of Three New Flavonoids from the Peels of Citrus unshiu

Three new flavonoids, 5,6,7,8,3′,4′‐hexamethoxyhomoflavone ( 1 ), 5,6,7,8,4′‐pentamethoxyhomoflavone ( 2 ) and 3,6,7,8,2′,5′‐hexamethoxyflavone ( 3 ) were isolated from the peels of mature fruits of Citrus unshiu Marcow (Rutaceae), together with the three known compounds 6,7,8,4′‐tetramethoxyflavone (=6,7,8‐trimethoxy‐2‐(4‐methoxyphenyl)‐4H‐1‐benzopyran‐4‐one), 3,5,7,8,2′,5′‐hexamethoxyflavone (=2‐(2,5‐dimethoxyphenyl)‐3,5,7,8‐tetramethoxy‐4H‐1‐benzopyran‐4‐one), and scopoletin (=7‐hydroxy‐6‐methoxy‐2H‐1‐benzopyran‐2‐one) of which the former two have never been isolated from natural resources, although they have been reported as synthetic compounds. The structures of 1 – 3 were elucidated on the basis of spectroscopic evidence, including 1D‐ and 2D‐NMR analysis.     

New Long‐Chain Esters and Adenine Analogs from the Leaves of Formosan Bridelia balansae

Six new compounds, including the two long‐chain esters balansenate I (=6,8,11‐trimethyldodecanoic acid (2E)‐3‐methylhexadec‐2‐enyl ester; 1 ) and balansenate II (=10,12,15‐trimethylhexadedecanoic acid (2E)‐3‐methylhexadec‐2‐enyl ester; 2 ), the eburicane‐like triterpenoid bridelone (=hexadecahydro‐4,4,10,13,14‐pentamethyl‐17‐(5‐methyl‐1,4‐dimethylenehexyl)‐3H‐cyclopenta[a]phenanthren‐3‐one; 3 ), the ‘deimino‐xanthine', bridelonine (=5‐(3‐methylbut‐2‐enyl)pyrrolo[3,4‐d]imidazole‐4,6(1H,5H)‐dione; 6 ), and the two adenine analogs 9‐(3‐methylbut‐2‐enyl)adenine ( 7 ) and 1‐(3‐methylbut‐2‐enyl)adenine ( 8 ), besides three known compounds, i.e., N⁶‐(3‐methylbut‐2‐enyl)adenine ( 4 ), 3‐(3‐methylbut‐2‐enyl)adenine ( 5 ), and adenine ( 9 ), were isolated from the leaves of Formosan Bridelia balansae. The novel skeleton of 6 consists of a fused pyrrolidine‐2,5‐dione and imidazole moiety. The already known adenines 7 and 8 were isolated for the first time from a plant. The structures of the isolated compounds were elucidated by spectroscopic analyses.     

Five New Eremophilane Sesquiterpenes from Ligularia przewalskii

Five new eremophilane‐type sesquiterpenes, 3β‐(acetyloxy)‐7‐hydroxynoreremophila‐6,9‐dien‐8‐one ( 1 ), 8β‐hydroxy‐2‐dehydroxyliguhodgsonal ( 2 ), 3β‐(acetyloxy)‐11‐methoxy‐8‐oxoeremophila‐6,9‐dien‐12‐oic acid ( 3 ), 3β‐(acetyloxy)‐11‐(2′‐methylbutanoyloxy)‐8‐oxoeremophila‐6,9‐dien‐12‐oic acid ( 4 ), and 3β‐(acetyloxy)‐6α‐hydroxyligularenolide ( 5 ), along with the three known compounds 6 – 8 , were isolated from the roots of Ligularia przewalskii. The structures of the new compounds were elucidated through spectral studies including HR‐EI‐MS, IR, and NMR data.     

Anthraquinone Derivatives and an Orsellinic Acid Ester from the Marine Alga‐Derived Endophytic Fungus Eurotium cristatum EN‐220

Cultivation of the fungal strain Eurotium cristatum EN‐220, an endophyte obtained from the marine alga Sargassum thunbergii, resulted in the isolation of one new anthraquinone glycoside, 3‐O‐(α‐D ‐ribofuranosyl)questinol ( 1 ) and one new orsellinic acid ester, cristatumside A ( 2 ), together with three known aromatic glycosides, 3‐O‐(α‐D ‐ribofuranosyl)questin ( 3 ), isotorachrysone 6‐O‐α‐D ‐ribofuranoside ( 4 ), and asperflavin ribofuranoside ( 5 ), as well as three anthraquinone derivatives, asperflavin ( 6 ), eurorubrin ( 7 ), and (+)‐variecolorquinone A ( 8 ). The structures of these compounds were determined by extensive analysis of their spectroscopic data, as well as by their comparison with those in the literature. Each of the isolated compounds was evaluated for its antimicrobial activity and brine shrimp lethality.     

Sesquiterpenoids and Phenylpropane Derivatives from Sonchus uliginosus

Six new compounds were isolated from the whole plant of Sonchus uliginosus, including three eudesmane‐type sesquiterpenoids (1β,6α)‐1,6,14‐trihydroxyeudesm‐3‐en‐12‐oic acid γ‐lactone ( 1 ), (1β,6α)‐1,6,14‐trihydroxyeudesma‐3,11(13)‐dien‐12‐oic acid γ‐lactone ( 2 ), and (1β,6α)‐1,6‐dihydroxy‐14‐O‐[(4‐hydroxyphenyl)acetyl]eudesma‐3,11(13)‐dien‐12‐oic acid γ‐lactone ( 3 ), and three phenylpropane derivatives, 4‐hydroxy‐γ,3,5‐trimethoxybenzenepropanol ( 6 ), γ,3,4,5‐tetramethoxybenzenepropanol ( 7 ), and γ,3,4,5‐tetramethoxybenzenepropanol acetate ( 8 ), together with the two known compounds 4 and 5 . The new structures were elucidated by means of spectroscopic methods, such as IR, EI‐MS, HR‐ESI‐MS, 1D‐ and 2D‐NMR, and by comparison of the spectroscopic data with those reported for structurally related compounds.     

The Constituents of Lindera Glauca

Twenty‐eight compounds including seven alkaloids, (+)‐3‐chloro‐N‐formylnornantenine ( 1 ), (+)‐N‐formylnornantenine ( 2 ), (+)‐boldine ( 3 ), (+)‐norboldine ( 4 ), (‐)‐norboldine ( 5 ), lycicamine ( 6 ), and tetrahydroberberine ( 7 ); four flavonoids, kaempferol ( 8 ), kaempferol‐3‐O‐arabinoside ( 9 ), quercetin ( 10 ), and quercetin‐3‐O‐rhamnoside ( 11 ); one butanolide, akolactone A ( 12 ); one p‐quinone, 2,6‐dimethoxy‐p‐quinone ( 13 ); one cyclohex‐2‐en‐1‐one, blumenol A ( 14 ); six benzenoids, methylparaben ( 15 ), p‐hydroxybenzoic acid ( 16 ), vanillic acid ( 17 ), syringic acid ( 18 ), 3,4,5‐trimethoxybenzoic acid ( 19 ), and 3‐(3,4‐dihydroxyphenyl) propionic acid ( 20 ); one diterpene, phytol ( 21 ); one triterpene, squalene ( 22 ); six steroids, (3‐sitosterol ( 23 ), β‐sitostenone ( 24 ), stigmasta‐4,22‐dien‐3‐one ( 25 ), 6β‐hydroxy‐β‐sitostenone ( 26 ), 6β‐hydroxystigmasterone ( 27 ), and β‐sitosteryl‐D‐glucoside ( 28 ) were isolated from the aerial part of Lindera glauca. These compounds were characterized and identified by physical and spectral method. All compounds were isolated for the first time from this plant. Among them, (+)‐3‐chloro‐N‐formylnornantenine ( 1 ) is a new one.     

Two New Chemical Constituents of Veratrum dahuricum (Turcz.) Loes. f.

Two new chemical constituents, one new steroid, neoveratrenone ( 1 ), and one new glycerol ester, 1‐[11‐(ferulyloxy)undecanoyl)]glycerol ( 2 ), were isolated and characterized from the roots and rhizomes of Veratrum dahuricum (Turcz .) Loes . f., together with five known compounds, i.e., hexacosanoic acid 2,3‐dihydroxypropyl ester ( 3 ), syringaresinol ( 4 ), prosapogenin A of dioscin ( 5 ), verapatulin ( 6 ), and oxyresveratrol ( 7 ). Their structures were established by extensive analysis of spectroscopic data as well as by comparison with literature reports. The compounds were evaluated for cytotoxic activity against three tumor cell lines of HepG‐2, HeLa, and K562/S.     

1H, 13C and 15N NMR spectroscopic characterization of unexpected degradation products of the nifedipine analogue bis(2‐cyanoethyl) 2,6‐dimethyl‐4‐(2‐nitrophenyl)‐1,4‐dihydro‐3,5‐pyridinedicarboxylate

In the course of saponification experiments with bis(2‐cyanoethyl) 2,6‐dimethyl‐4‐(2‐nitrophenyl)‐1,4‐dihydro‐3,5‐pyridinedicarboxylate ( 1 ), an analogue of the calcium channel blocker nifedipine, three unexpected degradation products were isolated. The compounds were identified as 3‐(2‐acetamido‐1‐carboxy‐1‐propenyl)‐1‐hydroxy‐2‐indolecarboxylic acid ( 3 ), 9‐hydroxy‐1,3‐dimethyl‐β‐carboline‐4‐carboxylic acid ( 4 ) and 6‐hydroxy‐2,4‐dimethyl‐5‐oxo‐5,6‐dihydrobenzo[c][2,7]naphthyridine‐1‐carboxylic acid ( 6 ). The structures of these compounds were deduced from one‐ and two‐dimensional ¹H, ¹³C and natural abundance ¹⁵N NMR experiments (¹H,¹H‐COSY, gs‐HSQC, gs‐HMBC, ¹⁵N gs‐HMBC), and corroborated by comparison of their NMR data with the respective data for structurally similar compounds. Copyright © 2002 John Wiley & Sons, Ltd.     

Isoprenoids and Flavonoids with Antimicrobial Activity from Ficus conraui Warburg (Moraceae)

A new triterpene, conrauidienol ( 1 ), and a new dihydroflavonol, conrauiflavonol ( 2 ), along with β‐amyrin acetate ( 3 ), betulinic acid ( 4 ), ursolic acid ( 5 ), 6β‐hydroxystigmasta‐4,22‐dien‐3‐one ( 6 ), 8‐prenylapigenin ( 7 ), β‐sitosterol glucoside ( 8 ), and 3,4′,5‐trihydroxy‐6″,6″‐dimethylpyrano[2,3‐g]flavone ( 9 ) were isolated from the stem barks of Ficus conraui Warburg (Moraceae). Their structures were elucidated by spectroscopic analysis. The hexane, AcOEt, and MeOH extracts, as well as the new isolated compounds exhibited selective antimicrobial activities varying from weak to moderate.     

The Chemical Constituents from the Callus Culture of Trewia nudiflora

Five ent‐atisane diterpenoids, including three new ones, i.e., (16α)‐17‐hydroxy‐ent‐atisan‐19‐oic acid methyl ester ( 1 ), (16α)‐17‐dihydroxy‐ent‐atisan‐19‐oic acid methyl ester ( 2 ), (16α)‐ent‐atisan‐16,17,19‐triol ( 3 ), and two known compounds, i.e., 17‐hydroxy‐ent‐atisan‐19‐oic acid ( 4 ), (16α)‐16,17‐dihydroxy‐ent‐atisan‐19‐al ( 5 ), together with one known diterpene glycoside, i.e., sumogaside, two known triterpenes, i.e., germanicone and (3β)‐β‐amyrin, three known phenolic compounds, i.e., (+)‐gallocatechin, (+)‐catechin, and gallic acid, and two known sterols, i.e., β‐sitosterol and daucosterol, were isolated from the callus cultures of Trewia nudiflora. Their structures were elucidated by spectroscopic analysis including 1D‐ and 2D‐NMR experiments. No maytansinoids were isolated or detected by LC‐ESI‐MS in the extracts of the calli, which suggests that the callus cultures can not produce maytansinoids under these conditions.     

Three New Compounds from Securidaca inappendiculata

Three new compounds, 2‐methoxy‐3,4‐(methylenedioxy)benzophenone ( 1 ), 4‐hydroxy‐2,3‐dimethoxybenzophenone ( 2 ), and 3‐hydroxy‐4,6‐dimethoxy‐9H‐xanthen‐9‐one ( 3 ), besides three known compounds were isolated from the roots of Securidaca inappendiculata. Their structures were established by spectroscopic means and X‐ray crystallographic diffraction analysis. The biogenetic relationships among these six compounds are discussed.     

New Lignans from the Roots of Taiwania cryptomerioides Hayata

The five new lignans designated 3′,4′‐de‐O‐methylenehinokinin ( 1 ), taiwaninolide ( 2 ), 8′‐hydroxysavinin ( 3 ), isoguamarol ( 4 ), and 4′‐O‐methylsalicifolin ( 5 ), as well as the new 4‐(3,4‐dimethoxybenzyl)dihydro‐3‐(4‐hydroxybenzyl)furan‐2(3H)‐one ( 6 ) were isolated from the roots of Taiwania cryptomerioides, besides the three known compounds hinokinin ( 8 ), savinin ( 9 ), and 3,4‐de‐O‐methylenehinokinin ( 7 ). The structures of the new constituents were elucidated through chemical and spectral studies. A compound previously isolated from the heartwood of Chamaecyparis obtusa var. formosana was assigned structure 1 ; however, this structure has now been revised to be 3,4‐de‐O‐methylenehinokinin ( 7 ).     

A Pair of Novel Heptentriol Stereoisomers from the Ascomycete Daldinia concentrica

A pair of novel heptentriol stereoisomers, hept‐6‐ene‐2,4,5‐triols 2 and 3 , were isolated from the culture broth of the ascomycete Daldinia concentrica (Bolton : Fries ) Cesati & De Notaris , besides three known compounds, i.e., 2,3‐dihydro‐5‐hydroxy‐2‐methyl‐4H‐1‐benzopyran‐4‐one ( 1 ), 3,5‐dihydroxy‐2‐(1‐oxobutyl)‐cyclohex‐2‐en‐1‐one ( 4 ), and pyroglutamic acid (=5‐oxo‐L ‐proline; 5 ). Their structures were determined by spectroscopic means, including 2D‐NMR (HMQC, HMBC, ¹H,¹H‐COSY).     

Oleanane Saponins from Rhizome of Anemone raddeana

Two new oleanolic acid‐type triterpenoid saponins, raddeanosides R₂₂ and R₂₃ ( 1 and 2 , resp.), together with four known saponins were isolated from the rhizome of Anemone raddeana Regel. The structures of the new compounds were elucidated as oleanolic acid 3‐O‐β‐D ‐glucopyranosyl(1→2)[β‐D ‐glucopyranosyl(1→4)]‐α‐L ‐arabinopyranoside ( 1 ) and oleanolic acid 3‐O‐α‐L ‐arabinopyranosyl(1→3)‐α‐L ‐rhamnopyranosyl(1→2)[β‐D ‐glucopyranosyl(1→4)]‐α‐L ‐arabinopyranoside ( 2 ). The four known compounds were identified as oleanolic acid 3‐O‐α‐L ‐arabinopyranoside ( 3 ), oleanolic acid 3‐O‐β‐D ‐glucopyranosyl(1→4)‐α‐L ‐arabinopyranoside ( 4 ), hederasaponin B ( 5 ), and hederacholchiside E ( 6 ) on the basis of chemical and spectral evidences. Compound 4 is reported for the first time from the Anemone genus, while the other three known compounds have been already found in this plant.     

Three New Sesquiterpenes from Laggera pterodonta

A new eremophilane sesquiterpene, (2β)‐2‐deoxo‐2‐methoxytessaric acid ( 1 ), and two new eudesmane sesquiterpenes, (3β,10α)‐3‐methoxyleudesma‐4,11(13)‐dien‐12‐oic acid ( 2 ) and (3α,4β,8α)‐4‐(acetyloxy)‐3‐(2,3‐dihydroxy)‐2‐methyl‐1‐oxobutoxy‐8‐hydroxyeudesm‐7(11)‐eno‐12,8‐lactone ( 3 ), along with the ten known compounds 4 – 13 were isolated from the aerial parts of Laggera pterodonta. The structures of the new compounds were elucidated by spectroscopic analyses, including 2D‐NMR data.     

New Phenolic Components from Daphne giraldii

Two new bis‐coumarins, namely daphnogitin ( 1 ), daphnogirin ( 2 ), and a flavan‐3‐ol derivative, 5‐O‐methylafzelechin ( 3 ), together with eleven known compounds, daphnetoxin, 1,2‐dihydrodaphnetoxin, daphnetin, daphnoretin, daphneticin, isodaphneticin, trans‐2,3‐dihydro‐3‐(4‐hydroxy‐3‐methoxyphenyl)‐2‐(hydroxymethyl)‐9H‐pyrano[2,3‐f]‐1,4‐benzodioxin‐9‐one (= demethoxyisodaphneticin; 4b ), (+)‐pinoresinol, acuminatin, (−)‐dihydrosesamin, and isosalicifoline, were isolated from the leaves and stems of Daphne giraldii. Compound 4b was isolated for the first time as a natural product, and 1,2‐dihydrodaphnetoxin, daphneticin, isodaphneticin, (+)‐pinoresinol, acuminatin, (−)‐dihydrosesamin, and isosalicifoline were isolated for the first time from Daphne giraldii. The structures of the three new compounds were elucidated by spectroscopic analysis.     

Scyphiphorins A and B,Two New Iridoid Glycosides from the Stem Bark of a Chinese Mangrove Scyphiphora hydrophyllacea

Two new iridoid glycosides, named scyphiphorins A ( 1 ) and B ( 2 ), together with four known compounds, geniposidic acid (=(1S,4aS,7aS)‐1‐(β‐D ‐glucopyranosyloxy)‐1,4a,5,7a‐tetrahydro‐7‐(hydroxymethyl)cyclopenta[c]pyran‐4‐carboxylic acid; 3 ), 4‐(4‐hydroxy‐3‐methoxybenzyl)butan‐2‐one, oleanolic acid (=(3β)‐3‐hydroxyolean‐12‐en‐28‐oic acid), and stigmasterol β‐D ‐glucoside (=(3β,22E)‐stigmasta‐5,22‐dien‐3‐yl β‐D ‐glucopyranoside), were isolated for the first time from the stem bark of a Chinese mangrove, Scyphiphora hydrophyllacea Gaertn . f. The structures of compounds 1 and 2 were determined as 10‐O‐benzoylgeniposidic acid and 10‐O‐[(2E,6R)‐8‐hydroxy‐2,6‐dimethyl‐1‐oxooct‐2‐en‐1‐yl]geniposidic acid, respectively, on the basis of spectroscopic data and chemical methods, including 2D NMR techniques.     

Cytotoxic Pentacyclic Triterpenoids from the Rhizome of Astilbe chinensis

Guided by in vitro antineoplastic tests, four cytotoxic pentacyclic triterpenoids, 3β‐hydroxyolean‐12‐en‐27‐oic acid ( 1 ), 3β‐hydroxyurs‐12‐en‐27‐oic acid ( 2 ), 3β,6β‐dihydroxyolean‐12‐en‐27‐oic acid ( 3 ), and 3β‐acetoxyolean‐12‐en‐27‐oic acid ( 4 ) were isolated from the rhizome of Astilbe chinensis. Their structures were determined on the basis of chemical evidence and extensive spectroscopic methods including one‐dimensional and two‐dimensional NMR. These compounds showed cytotoxic activities against HO‐8910, Hela and HL60 cell lines. In addition, β‐sitosterol palmitate, daucosterol, and β‐sitosterol have also been isolated.     

New Cytotoxic Meroterpenoids from the Plant Endophytic Fungus Pestalotiopsis fici

Pestalofones I – K ( 1 – 3 ), three new dimeric meroterpenoids with 2‐(7‐benzoyl‐2,3‐dihydrobenzofuran‐2‐yl)‐1‐phenylethan‐1‐one (in 1 ) and 2‐(7‐benzoyl‐2,3‐dihydrobenzofuran‐2‐yl)‐1‐(3,8‐dioxatricyclo[5.1.0.0^2,4]oct‐4‐yl)ethan‐1‐one (in 2 and 3 ) skeletons, were isolated from the solid cultures of the plant endophytic fungus Pestalotiopsis fici. The structures of 1 – 3 were elucidated by NMR experiments. Compound 1 was found to be present as a racemic mixture. The absolute configurations of 2 and 3 were deduced by analogy to the previously isolated metabolites pestalofones G and H ( 4 and 5 ) from the same fungus. Biogenetically, compounds 1 – 3 are derived from the same precursors (co‐isolated compounds 9 and 10 ) as the previously isolated compounds 4 – 8 . Compounds 2 and 3 showed weak cytotoxic activities against four human tumor cell lines T24, HeLa, A549, and MCF‐7.