Diterpenes from Xylopia langsdorffiana

The phytochemical investigation of Xylopia langsdorffiana A.St.‐Hil. & Tul . led to the isolation of eight diterpenes, i.e., of the four new compounds (5β,7β,8α,9β,10α,12α)‐atisane‐7,16‐diol 7‐acetate ( 1 ), named xylodiol 7‐acetate, (5β,8α,9β,10α,12α)‐16‐hydroxyatisan‐7‐one ( 2 ), named xylopinone, (3α,12Z)‐3‐hydroxy‐ent‐labda‐8(20),12,14‐trien‐18‐oic acid ( 3 ), named labdorffianic acid A, and 8,20‐epoxy‐13‐hydroxy‐ent‐labd‐14‐en‐18‐oic acid ( 4 ), named labdorffianic acid B, and of the four known compounds 5 – 8 , i.e., ent‐kauran‐16‐ol, ent‐kaur‐16‐en‐19‐oic acid, ent‐kaur‐16‐en‐19‐ol, and ent‐trachyloban‐18‐oic acid. The structures were established by IR, HR‐ESI‐MS, and NMR data analysis with the aid of 2D techniques.     

Four New Podocarpane‐Type Trinorditerpenes from Aleurites moluccana

Four new podocarpane‐type trinorditerpenenes, (5β,10α)‐12,13‐dihydroxypodocarpa‐8,11,13‐trien‐3‐one ( 1 ), (5β,10α)‐12‐hydroxy‐13‐methoxypodocarpa‐8,11,13‐trien‐3‐one ( 2 ), (5β,10α)‐13‐hydroxy‐12‐methoxypodocarpa‐8,11,13‐trien‐3‐one ( 3 ), and (3α,5β,10α)‐13‐methoxypodocarpa‐8,11,13‐triene‐3,12‐diol ( 4 ), together with four known diterpenes, 12‐hydroxy‐13‐methylpodocarpa‐8,11,13‐trien‐3‐one ( 5 ), spruceanol ( 6 ), ent‐3α‐hydroxypimara‐8(14),15‐dien‐12‐one ( 7 ), and ent‐3β,14α‐hydroxypimara‐7,9(11),15‐triene‐12‐one ( 8 ), were isolated from the twigs and leaves of Aleurites moluccana. Their structures were elucidated by means of comprehensive spectroscopic analyses, including NMR and MS. Except 8 , all compounds were evaluated for their cytotoxicity; compound 4 exhibited moderate inhibitory activity against Raji cells with an IC₅₀ value of 4.24 μg/ml.     

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.     

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.     

Chemical Constituents from Annona Glabra

A new kaurane diterpenoid, annoglabasin G (16α‐hydro‐19‐acetoxy‐ent‐kauran‐17‐al) ( 1 ), along with 27 compounds including 18 kaurane diterpenoids, 16β‐hydro‐ent‐kauran‐17‐oic acid ( 2 ), 16α‐hydro‐ent‐kauran‐17‐oic acid ( 3 ), 19‐nor‐ent‐kauran‐4α‐ol‐17‐oic acid ( 4 ), 16α‐hydro‐19‐ol‐ent‐kauran‐17‐oic acid ( 5 ), ent‐kaur‐16‐en‐19‐oic acid ( 6 ), 16α‐hydroxy‐ent‐kauran‐19‐oic acid ( 7 ), 16α,17‐dihydroxy‐ent‐kauran‐19‐oic acid ( 8 ), 16β,17‐dihydroxy‐ent‐kauran‐19‐oic acid ( 9 ), 16α‐hydro‐ent‐kauran‐17,19‐dioic acid ( 10 ), 16β‐hydroxy‐17‐acetoxy‐ent‐kauran‐19‐oic acid ( 11 ), 16β‐hydro‐17‐hydroxy‐ent‐kauran‐19‐al ( 12 ), 16α‐hydro‐17‐hydroxy‐ent‐kauran‐19‐al ( 13 ), 16β,17‐dihydroxy‐ent‐kauran‐19‐al ( 14 ), 16α‐hydro‐19‐al‐ent‐kauran‐17‐oic acid ( 15 ), 16α‐hydro‐17‐acetoxy‐ent‐kauran‐19‐al ( 16 ), 16α‐hydro‐19‐acetoxy‐ent‐kauran‐17‐oic acid ( 17 ), ent‐kaur‐15‐en‐19‐oic acid ( 18 ) and ent‐kaur‐15‐en‐17‐ol‐19‐oic acid ( 19 ); four acetogenins, annomontacin ( 20 ), annonacin ( 21 ), isoannonacinone ( 22 ) and squamocin ( 23 ); four steroids, β‐sitosterol ( 24 ), stigmasterol ( 25 ), β‐sitosteryl‐D‐glucoside ( 26 ) and stigmasteryl‐D‐glucoside ( 27 ) and one oxoaporphine, liriodenine ( 28 ), were isolated from the fresh fruits of Annona glabra. These compounds were characterized and identified by physical and spectral evidence.     

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.     

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.     

Thrombin Inhibitory Constituents from Duranta repens

The C‐alkylated flavonoids 3,7,4′‐trihydroxy‐3′‐(4‐hydroxy‐3‐methylbutyl)‐5,6‐dimethoxyflavone ( 1 ), 3,7‐dihydroxy‐3′‐(4‐hydroxy‐3‐methylbutyl)‐5,6,4′‐trimethoxyflavone ( 2 ) and the trans‐clerodane diterpenoids 6β‐hydroxy‐15,16‐epoxy‐5β,8β,9β,10α‐cleroda‐3,13(16),14‐trien‐18‐oic acid ( 3 ) and 2β‐hydroxy‐15,16‐epoxy‐5β,8β,9β,10α‐cleroda‐3,13(16),14‐trien‐18‐oic acid ( 4 ) were isolated from Duranta repens. Their structures and the relative configuration of 3 and 4 were determined by spectroscopic methods (¹H‐ and ¹³C‐NMR, IR, and MS) and 2D‐NMR experiments. The known flavonoid 5 is also reported for the first time from this species. The compounds 1 , 3 , and 5 showed significant enzyme‐inhibitory activity against thrombin.     

Triterpenoids from the Stems of Momordica charantia

Two new cucurbitane triterpenes, (23E)‐7β‐methoxycucurbita‐5,23,25‐trien‐3β‐ol ( 1 ) and 23,25‐dihydroxy‐5β,19‐epoxycucurbit‐6‐ene‐3,24‐dione ( 2 ), and a new D : C‐friedooleanane triterpene, 3α‐[(E)‐feruloyloxy]‐D : C‐friedooleana‐7,9(11)‐dien‐29‐oic acid ( 3 ), together with two known D : C‐friedooleanane triterpenes, 3β‐[(E)‐feruloyloxy]‐D : C‐friedooleana‐7,9(11)‐dien‐29‐oic acid ( 4 ) and 3‐oxo‐D : C‐friedooleana‐7,9(11)‐dien‐29‐oic acid ( 5 ), were isolated from the stems of Momordica charantia. The structures of the new compounds 1 – 3 were determined by spectroscopic methods.     

Two New Diterpenoids from Callicarpa pedunculata

Two new diterpenoids, pedunculatic acid A (= (4R,5α,7α)‐7‐ethoxy‐9β,13β‐dioxyabiet‐8(14)‐en‐18‐oic acid; 1 ) and pedunculatic acid B (= (4S,5α,12β)‐8β,14β‐epoxy‐12‐hydroxy‐11‐oxototaran‐19‐oic acid; 2 ), together with three known sesquiterpenoids, were isolated from the Chinese medicinal herb Callicarpa pedunculata R. Brown . Their structures were elucidated by spectroscopic analyses, including 1D‐ and 2D‐NMR, and by high‐resolution mass spectrometry.     

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 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.     

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.     

Chemical Constituents from the Pericarp of Trewia nudiflora

Three new ent‐atisane diterpenes, i.e., 17‐hydroxy‐ent‐atisan‐19‐oic acid ( 1 ), 17‐hydroxy‐ent‐atisan‐19‐oic acid methyl ester ( 2 ), and 16α,17‐dihydroxy‐ent‐atisan‐19‐al ( 3 ), together with five known phenolic compounds, i.e., gallic acid, ethyl gallate, protocatechuic acid, 3,4,4′‐tri‐O‐methylellagic acid, and α‐tocopherol, and two other known compounds, i.e., trans‐cinnamic acid and taraxerone, were isolated from the pericarp of Trewia nudiflora collected in Xishuangbanna, Yunnan Province, China. Their structures were elucidated by spectroscopic analysis including 1D‐ and 2D‐NMR. Trace amounts of maytansinoids were isolated by antifungal‐activity‐guided fractionation and determined by LC‐ESI‐MS analysis; they were prominent antifungal constituents in the pericarp of Trewia nudiflora.     

A Benzofuranoid and Two Clerodane Diterpenoids from Pulicaria wightiana

Methyl 5‐formyl‐1‐benzofuran‐6‐carboxylate ( 1 ) and the two clerodane diterpenes, methyl 6‐oxocleroda‐3,13‐dien‐15,16‐olid‐18‐oate ( 2 ) and 2β‐(2‐methylbutanoyl)cleroda‐3,13‐dien‐15,16‐olid‐18‐oic acid ( 3 ), together with 15 known compounds, were isolated from the aerial parts of Pulicaria wightiana. The structures of the new compounds 1, 2 , and 3 were established by spectroscopic (mainly 1D‐ and 2D‐NMR) methods.     

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.     

Three New ent‐Trachylobane Diterpenoids from Co‐cultures of the Calli of Trewia nudiflora and Fusarium sp. WXE

Five diterpenoids, including three new ent‐trachylobane diterpenoids, i.e., (3α)‐3‐hydroxy‐ent‐trachylobane‐17,19‐dioic acid 19‐methyl ester ( 1 ), ent‐trachylobane‐17,19‐dioic acid 19‐methyl ester ( 2 ), ent‐trachylobane‐17,19‐dioic acid ( 3 ), and two known atisane‐type ones, i.e., (16α)‐16,17‐dihydroxy‐ent‐atisan‐19‐oic acid methyl ester ( 4 ), and 17‐hydroxy‐ent‐atisan‐19‐oic acid methyl ester ( 5 ), were isolated from the co‐culture extract of the calli of Trewia nudiflora and its endophytic fungus Fusarium sp. WXE. Their structures were elucidated by spectroscopic analyses, including 1D‐ and 2D‐NMR experiments, and HR‐Q‐TOF mass spectrometry. The antitumor and antibacterial properties of the new compounds were evaluated.     

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.     

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.     

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.