Lanostane Triterpenes from Ceriporia lacerate HS‐ZJUT‐C13A,a Fungal Endophyte of Huperzia serrata

Two new lanostane triterpenes, 3β‐acetoxy‐15α‐hydroxylanosta‐8,24‐dien‐21‐oic acid ( 1 ) and 3β‐acetoxylanosta‐7,9(11),24‐trien‐21‐oic acid ( 2 ), along with the four known analogs, 3 – 6 , were isolated from the culture broth of Ceriporia lacerate HS‐ZJUT‐C13A, a fungal endophyte residing in the stems of the traditional Chinese herb Huperzia serrata. The structures of the new compounds 1 and 2 were established by spectroscopic methods, including UV, IR, HR‐ESI‐MS, and extensive 1D‐ and 2D‐NMR techniques. To the best of our knowledge, this is the first report on triterpene metabolites from the genus Ceriporia.     

Novel Sesquiterpenoids from Siegesbeckia orientalis

Five new sesquiterpenoids, namely, 8β‐(angeloyloxy)‐4β,6α,15‐trihydroxy‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 1 ), 4β,6α,15‐trihydroxy‐8β‐(isobutyryloxy)‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 2 ), 11,12,13‐trinorguai‐6‐ene‐4β,10β‐diol ( 3 ), (1(10)E,4E,8Z)‐8‐(angeloyloxy)‐6α,15‐dihydroxy‐14‐oxogermacra‐(1(10),4,8,11(13)‐tetraen‐12‐oic acid 12,6‐lactone ( 9 ), and (1(10)E,4β)‐8β‐(angeloyloxy)‐6α,14,15‐trihydroxygermacra‐1(10),11(13)‐dien‐12‐oic acid 12,6‐lactone ( 11 ), and three new artifacts, (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4,11(13)‐trien‐12‐oic acid 12,6‐lactone ( 6 ), (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α,13‐diethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 7 ), and (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐13‐methoxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 8 ), together with the three known sesquiterpenoids 4, 5 , and 10 , were isolated from the aerial parts of Siegesbeckia orientalis L. Their structures were established by spectral methods, especially 1D‐ and 2D‐NMR spectral methods.     

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.     

Two New Labdane‐Type Diterpene Acids from the Wood of Cunninghamia konishii

Two new labdane‐type diterpene acids, (12S)‐12‐hydroxylabda‐8(17),13(16),14‐trien‐18‐oic acid ( 1 ) and (12R)‐12‐hydroxy‐15,16‐epoxylabda‐8(17),13‐dien‐18‐oic acid ( 2 ), along with a known labdane‐type diterpene, (11E)‐15,16‐bisnor‐13‐oxolabda‐8(17),11‐dien‐19‐oic acid ( 3 ), were isolated from the MeOH extract of the wood of Cunninghamia konishii. Their structures were determined by analysis of spectroscopic data and comparison with the data of known analogs.     

Cucurbitane Triterpenoids from the Fruit Pulp of Momordica charantia and Their Cytotoxic Activity

Two new cucurbitane‐type triterpenes, 25‐methoxycucurbita‐5,23(E)‐diene‐3β,19‐diol ( 1 ) and 7β‐ethoxy‐3β‐hydroxy‐25‐methoxycucurbita‐5,23(E)‐dien‐19‐al ( 2 ), together with three known cucurbitane‐type triterpenes, 3β,7β,25‐trihydroxycucurbita‐5,23(E)‐dien‐19‐al ( 3 ), (23E)‐3β‐hydroxy‐7β,25‐dimethoxycucurbita‐5,23‐dien‐19‐al ( 4 ), and 3β‐hydroxy‐25‐methoxycucurbita‐6,23(E)‐dien‐19,5β‐olide ( 5 ), were isolated from the fruit pulp of Momordica charantia. The structures of two new compounds were elucidated on the basis of 1D and 2D NMR, MS, IR, optical rotation. Among these isolates, compounds 1 , 2 , and 5 showed slight cytotoxic activity against the SK‐Hep 1 cell line with IC₅₀ values of 33.1, 24.3, and 38.7 μM, respectively.     

Euphane Triterpenes from the Bark of Broussonetia papyrifera

Four new euphane triterpenes, (3β)‐3‐(acetyloxy)eupha‐7,25‐dien‐24‐one ( 1 ), (3β,24R)‐3‐(acetyloxy)eupha‐7,25‐dien‐24‐ol ( 2 ), (3β,24S)‐eupha‐7,25‐diene‐3,24‐diol ( 3 ), and (3β,24R)‐eupha‐7,25‐diene‐3,24‐diol ( 4 ) were isolated from the barks of Broussonetia papyrifera, a tree whose roots, barks, and fruits were used as herbal drugs in China. The structures of 1 – 4 were elucidated on the basis of spectroscopic evidence and chemical methods.     

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.     

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.     

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.     

Triterpenoids from Rhaponticum Uniflorum

The isolation and identification of twenty‐one components (including four new triterpenoid saponins and one new triterpenoid acid) from the root of Rhaponticum uniflorum (L.) DC. (Compositae) are described. Their structures were determined on the basis of spectral analysis and chemical trans formation. The new compounds were identified as 3‐O‐α‐L‐arabinopyranosyl‐urs‐12,18(19)‐dien‐28‐oic acid β‐D‐glucopyranosyl ester, 3β‐ hydroxyurs‐12,18(19)‐dien‐28‐oic acid β‐D‐glucopyranosyl ester, 3β‐hydroxyurs‐12,19(29)‐dien‐28‐oic acid β‐D‐glucopyranosylester, 3‐O‐α‐L‐arabinopyranosyl‐urs‐9(11),12‐dien‐28‐oic acid β‐D‐glucopyranosyl ester and 2 α,3 α, 19α,25‐tetrahydroxyurs‐12‐en‐23,28‐dioic acid.     

Triterpenoids from the Mangrove Plant Hibiscus tiliaceus

Three new triterpenoids with the rarely occurring nigrum skeleton, namely (20E)‐22‐hydroxynigrum‐20‐en‐3‐one ( 1 ), 21β‐hydroxynigrum‐22(29)‐en‐3‐one ( 2 ), and 21α‐hydroxynigrum‐22(29)‐en‐3‐one ( 3 ), were isolated from the mangrove plant Hibiscus tiliaceus. Additionally, five known triterpenoids including friedelin ( 4 ), 12‐oleanen‐3β‐ol ( 5 ), 3β‐hydroxy‐12‐oleanen‐28‐oic acid ( 6 ), 20(29)‐lupen‐3β,28‐diol ( 7 ), and cucurbita‐5,23‐dien‐3β,25‐diol ( 8 ) were also isolated and identified. The latter structures were elucidated by a detailed NMR and MS analyses, as well as by comparison with reported literature data.     

Terpenoids from Two Dicranopteris Species

Two new compounds, (6S,13S)‐6‐{[β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl]oxy}cleroda‐3,14‐dien‐13‐ol ( 1 ) and kadsuric acid 3‐methyl ester ( 2 ), together with nine known compounds, (6S,13E)‐6‐{[β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl]oxy}cleroda‐3,13‐dien‐15‐ol ( 3 ), (6S,13S)‐6‐[6‐O‐acetyl‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl]oxy}‐13‐{[α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐fucopyranosyl]oxy}cleroda‐3,14‐diene ( 4 ), (6S,13S)‐6‐{[6‐O‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl]oxy}‐13‐{[α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐fucopyranosyl]oxy}cleroda‐3,14‐diene ( 5 ), 15‐hydroxydehydroabietic acid ( 6 ), 15‐hydroxylabd‐8(17)‐en‐19‐oic acid ( 7 ), junicedric acid ( 8 ), (4β)‐kaur‐16‐en‐18‐oic acid ( 9 ), (4β)‐16‐hydroxykauran‐18‐oic acid ( 10 ), and (4β,16β)‐16‐hydroxykauran‐18‐oic acid ( 11 ) were isolated from the fronds of Dicranopteris linearis or D. ampla. Their structures were established by extensive 1D‐ and 2D‐NMR spectroscopy. Compounds 1 and 3 – 8 showed no anti‐HIV activities.     

Sesquiterpenoids and Lignans from Ligularia virgaurea spp. oligocephala

From the BuOH extract of the whole plant of Ligularia virgaurea spp. oligocephala, a series of sesquiterpenes, sesquiterpene glycosides, and lignan glycosides were isolated, including the three new compounds (1α)‐1‐hydroxy‐8‐oxo‐eremophila‐6,9‐dien‐12‐oic acid ( 1 ), 8‐[(β‐D ‐glucopyranosyl)oxy]eremophila‐1(10),8,11‐trien‐2‐one ( 2 ), and 4‐[(β‐D ‐glucopyranosyl)oxy]pinoresinol ( 4 ). Their structures were elucidated by 1D‐ and 2D‐NMR as well as HR‐ESI‐MS analyses, and by comparison of the spectroscopic data with those reported for structurally related compounds.     

Bruceines K and L from the Ripe Fruits of Brucea javanica

Bruceine K ( 1 ), a pentacyclic C₂₀‐quassinoid bearing a unique 12,20‐epoxy moiety, and bruceine L ( 2 ), along with the ten known compounds (6S,7E)‐6,9,10‐trihydroxy‐ and (6S,7E)‐6,9‐dihydroxymegastigma‐4,7‐dien‐3‐one ( 3 and 4 , resp.), cleomiscosins A–C, luteoline, quercetine, bruceantinol, pinoresinol, and thevetiaflavone, were isolated from the ripe fruits of Brucea javanica. Bruceines K ( 1 ) and L ( 2 ) were determined to be (1β,2α,11β,12β,14ξ,15β)‐12,20‐epoxy‐1,2,11,13,14,15‐hexahydroxypicras‐3‐en‐16‐one and (1β,2α,11β,12β,15β)‐13,20‐epoxy‐1,2,11,12‐tetrahydroxy‐16‐oxo‐15‐(senecioyloxy)picras‐3‐en‐21‐oic acid methyl ester (senecioic acid=3‐methylbut‐2‐enoic acid), respectively, on the basis of NMR (¹H‐ and ¹³C‐NMR, DEPT, ¹H,¹H‐COSY, NOESY, HMQC, and HMBC) and ESI‐MS data. Among the known compounds, (6S,7E)‐6,9,10‐trihydroxy‐ and (6S,7E)‐6,9‐dihydroxymegastigma‐4,7‐dien‐3‐one ( 3 and 4 , resp.), cleomiscosin C, luteoline, quercetine, and thevetiaflavone were isolated for the first time from the Brucea plants.     

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.     

Two New 3,4‐Seco‐ent‐kaurenes and Other Constituents from the Costa Rican Endemic Species Croton megistocarpus

Following our phytochemical studies of Costa Rican plants, we report the isolation of two new 3,4‐seco‐ent‐kaurenes from the aerial parts of Croton megistocarpus (Euphorbiaceae). The structures of the two compounds were elucidated as 14‐[(2‐methylbutanoyl)oxy]‐3,4‐seco‐ent‐kaura‐4(19),16‐dien‐3‐oic acid ( 1 ) and 14‐{[(2Z)‐2‐methylbut‐2‐enoyl]oxy}‐3,4‐seco‐ent‐kaura‐4(19),16‐dien‐3‐oic acid ( 2 ). In addition, seven known diterpene clerodanes were also isolated and identified. The structures of the compounds were elucidated by spectroscopic methods, including HR‐MS, ¹H‐NMR, ¹³C‐NMR, COSY, HMQC, HMBC, and NOESY experiments.     

Chemical Constituents from Craibiodendron yunnanense

A new triterpene, (3β,12β)‐taraxast‐20(30)‐ene‐3,12‐diol (=(3β,12β,18α,19α)‐urs‐20(30)‐ene‐3,12‐diol; 1 ), together with the known compounds ursolic acid, α‐amyrin, β‐amyrin, (2α,3β)‐2,3‐dihydroxyursa‐5,12‐dien‐28‐oic acid, (2α,3β)‐2,3,23‐trihydroxyurs‐12‐en‐28‐oic acid, (2S,3S,4R,8Z)‐1‐O‐(β‐D ‐glucopyranosyl)‐2‐{[(2R)‐2‐hydroxydocosanoyl]amino}octadec‐8‐ene‐1,3,4‐triol, and (2S,3S,4R,8Z)‐1‐O‐(β‐D ‐glucopyranosyl)‐2‐[(palmitoyl)amino]octadec‐8‐ene‐1,3,4‐triol, and quercetin 3‐(β‐D ‐glucopyranoside) were isolated from the leaves of Craibiodendron yunnanense. Their structures were established on the basis of spectral evidence. The last four compounds were identified for the first time in this plant.     

Chemical Constituents from the Roots of Schnabelia tetradonta

The new rearranged‐abietane diterpene 1 , the four new triterpenoids 2 – 5 , and the new aminoethylphenyl oligoglycoside 6 , besides 19 known compounds, were isolated from the roots of Schnabelia tetradonta, a Chinese endemic herb. The structures of the new compounds were elucidated on the basis of spectroscopic evidence as 12,17‐epoxy‐11,14,16‐trihydroxy‐17(15→16)‐abeo‐abieta‐8,11,13,15‐tetraen‐7‐one ( 1 ), 21β‐(β‐D ‐glucopyranosyloxy)‐2α,3α‐dihydroxyolean‐12‐en‐28‐oic acid ( 2 ), 2β,3β,16β‐trihydroxy‐15‐oxo‐28‐norolean‐12‐en‐23‐oic acid ( 3 ), 3β‐[(4‐O‐acetyl‐β‐D ‐glucopyranuronosyl)oxy]‐2β,16β‐dihydroxy‐28‐norolean‐15‐oxo‐12‐en‐23‐oic acid ( 4 ), 3β‐[(4‐O‐acetyl‐6‐O‐methyl‐β‐D ‐glucopyranuronosyl)oxy]‐2β,16β‐dihydroxy‐15‐oxo‐28‐norolean‐12‐en‐23‐oic acid ( 5 ), and 4‐[2‐(acetylamino)ethyl]phenyl O‐6‐O‐[(Z)‐p‐methoxycinnamoyl]‐β‐D ‐glucopyranosyl‐(1→2)]‐O‐[β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐acetyl‐α‐L ‐rhamnopyranoside ( 6 ), respectively.     

A New 30‐Noroleanane Saponin from Wedelia chinensis

A novel 30‐nortriterpenoid saponin, (3β)‐3‐hydroxy‐30‐noroleana‐12,20(29)‐dien‐28‐oic acid 3‐(β‐D ‐glucopyranosiduronic acid 6‐methyl ester) ( 1 ), and a known compound, (3β)‐oleanolic acid 3‐(β‐D ‐glucopyranosiduronic acid 6‐methyl ester) ( 2 ), were isolated from the aerial parts of Wedelia chinensis. The structures were established by their spectral data including ¹H‐ and ¹³C‐NMR, ¹H,¹H‐COSY, HMBC, HSQC, NOESY, and HR‐FAB‐MS data.     

Two New Triterpene and a New Nortriterpene Glycosides from Phlomis viscosa

The isolation and structure elucidation of two new oleanane‐type triterpene glycosides, 29‐(β‐D ‐glucopyranosyloxy)‐2α,3β,23‐trihydroxyolean‐12‐en‐28‐oic acid (=(2α,3β,4α,29α)‐29‐(β‐D ‐glucopyranosyloxy)‐2,3,23‐trihydroxyolean‐12‐en‐28‐oic acid; 1 ) and its C(20)‐epimer, 30‐(β‐D ‐glucopyranosyloxy)‐2α,3β,23‐trihydroxyolean‐12‐en‐28‐oic acid (=(2α,3β,4α,29β)‐29‐β‐D ‐glucopyranosyloxy)‐2,3,23‐trihydroxyolean‐12‐en‐28‐oic acid; 2 ), and a novel nortriterpene glycoside, (17S)‐2α,18β,23‐trihydroxy‐3,19‐dioxo‐19(18→17)‐ abeo‐28‐norolean‐12‐en‐25‐oic acid β‐D ‐glucopyranosyl ester (=(1R,2S,4aS,4bR,6aR,7R,9R,10aS,10bS)‐3,4,4a,4b,5,6,6a,7,8,9,10,10a,10b,11‐tetradecahydro‐1‐hydroxy‐7‐(hydroxymethyl)‐3′,4′,4a,4b,7‐pentamethyl‐2′,8‐ dioxospiro[chrysene‐2(1H),1′‐cyclopentane]‐10a‐carboxylic acid β‐D ‐glucopyranosyl ester; 3 ) from Phlomis viscosa (Lamiaceae) are reported. The structures of the compounds were asigned by means of spectroscopic (IR, 1D‐ and 2D‐NMR, and LC‐ESI‐MS) and chemical (acetylation) methods.