Secondary Metabolites from the Fungus Monascus purpureus and Evaluation of Their Cytotoxic Activity

Investigation of the 95% EtOH extract of red yeast rice fermented with the fungus Monascus purpureus BCRC 31615 has led to the isolation and structure elucidation of four new compounds, including one new azaphilone analog, monascuspurpurone ( 1 ), a new isocoumarin, monaschromone ( 2 ), a new furan‐3‐one derivative, 2‐dodecyl‐5‐(2‐methoxyethyl)‐2‐methylfuran‐3(2H)‐one ( 3 ), and a new alkaloid, methyl 4‐[(E)‐2‐acetyl‐4‐oxoundec‐1‐enyl]‐6‐propylnicotinate ( 4 ), together with seven known compounds. The structures of all isolates were elucidated on the basis of extensive spectroscopic analyses and comparison with literature data. Compounds 1 – 4 were tested for their cytotoxicity against the MCF‐7, NCI‐H460, and SF‐268 cell lines using the MTT (=3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐2H‐tetrazolium bromide) assay. Among them, compounds 1 and 4 were found to have moderate cytotoxic effects against these three cell lines in vitro.     

Lagotoside: A New Phenylpropanoid Glycoside from Lagotis stolonifera

From the aerial parts of Lagotis stolonifera (Scrophulariaccae), a new phenylpropanoid glycoside, lagotoside ( 8 ), and the three known glycosides ehrenoside ( 5 ), verbascoside (= acteoside; 6 ), and plantamajoside ( 7 ) were isolated, together with the four known iridoid glucosides aucubin ( 1 ), catalpol( 2 ), globularin ( 4 ), and lythantosalin ( 3 ). The structure of the new compound 8 was elucidated on the basis of chemical and spectral data as 2-(3-hy-droxy-4-methoxyphenyl)ethyl O-[α-L -arabinopyranosyl-(1 → 2)]-O-[α-L -rhamnopyranosyl-(1 → 3)]-4-O-feruloyl-β-D -glucopyranoside.     

Three New Monoterpene Alkaloids and a New Caffeic Acid Ester from Incarvillea mairei var. multifoliolata

Three new monoterpene alkaloids, mairine A ( 1 ), mairine B ( 2 ), and mairine C ( 3 ), and a new caffeic acid ester, 2‐(1‐hydroxy‐4,4‐dimethoxycyclohexyl)ethyl caffeate ( 4 ), were isolated from the EtOH extract of the whole plants of Incarvillea mairei var. multifoliolata. The structures of these compounds were established on the basis of 1D‐ and 2D‐NMR and HR‐ESI‐MS analysis.     

New Polyphenols and Triterpene from the Pseudobulbs of Pleione Formosana

Three new polyphenolic compounds including a dihydrophenanthrene, pleioanthrenin ( 1 ), two bibenzyls, pleiobibenzynin A ( 2 ) and B ( 3 ), and a new cycloartane triterpenoid, (24R)‐cyclomargenyl p‐coumarate ( 4 ), together with eight known compounds, were isolated from the pseudobulbs of Pleione formosana. The structures of the new compounds were elucidated by extensively spectroscopic analysis.     

Constituents from Rubia Ustulata Diels and R. Yunnanensis Diels and Their Antiplatelet Aggregation Activity

A new anthraquinone glycoside, rubiayannone‐A ( 1 ), and a new coumarin, rubilatin‐A ( 2 ), together with twenty‐two known compounds were isolated and characterized from the roots of Rubia ustulata. A new anthraquinone, 2‐carbomethoxyanthraquinone ( 3 ), and rubiayannone‐A, 2‐formylanthraquinone were obtained from the roots of R. yunnanensis. The structures of those compounds were elucidated by spectroscopic methods. The antiplatelet aggregation activity of the isolated compounds 1, 4～6 were also discussed.     

Characterization of Eight New Secondary Metabolites from the Mutant Strain G‐444 of Tubercularia sp. TF5

Eight new metabolites, including five new sesquiterpenoids, 10,11‐epoxyguaian‐10‐ol ( 1 ), 10,11‐epoxyguaian‐13‐ol ( 2 ), a new backbone sesquiterpene rearranged from guaiane ( 3 ), two 1,5 : 1,10‐disecoguaianes, 4 and 5 , two new dihydroisocoumarins, 7‐chloromellein‐4‐ol ( 6 ) and 7‐chloromellein‐5‐ol ( 7 ), and one new tetralone, 7‐chloroscytalone ( 8 ), were isolated from the mutant strain G‐444 of Tubercularia sp. TF5, an endophytic fungus of Taxus mairei, along with ten known compounds, 3,4‐dihydro‐4,8‐dihydroxy‐2H‐naphthalen‐1‐one ( 9 ), (3R,4S)‐4‐hydroxymellein ( 10 ), 5‐formylmellein ( 11 ), 5‐carboxymellein ( 12 ), sporogen‐AO1 ( 13 ), tuberculariols A ( 14 ) and B ( 15 ), hymatoxin E ( 16 ), 4‐oxo‐4H‐pyran‐3‐acetic acid ( 17 ), and penicillic acid ( 18 ). Their structures were elucidated by spectroscopic analyses including HR‐ESI‐MS, 1D‐ and 2D‐NMR (HMQC, HMBC, ¹H,¹H‐COSY and NOESY). The antimicrobial activities of 1 – 8 were evaluated, but none showed any substantial effect.     

Iridoid Glycosides and Phenolic Compounds from the Flowers of Vitex agnus‐castus

A new and rare type of iridoid glycoside, agnusoside ( 1 ), a new caffeoylquinic acid derivative, castusic acid ( 2 ), and a new sugar ester, 1,2‐di‐(4‐hydroxybenzoyl)‐β‐glucopyranose ( 3 ), along with ten known compounds belonging to iridoid glycosides (agnuside, trans‐eurostoside), caffeoylquinic acid derivatives (chlorogenic acid and isochlorogenic acid A), flavonoids (isoorientin, isovitexin, kaempferol 3‐O‐sophoroside, luteolin 6‐C‐(2′′‐O‐trans‐caffeoyl)glucopyranoside, and simple phenolic acids (4‐hydroxybenzoic acid, 3,4‐dihydroxybenzoic acid), chemical classes were isolated from the flowers of Vitex agnus‐castus. The structures of the isolates were established by extensive 1D‐ and 2D‐NMR spectroscopic analysis as well as HR‐ESI‐MS. Agnusoside ( 1 ) represents an unusual type of iridoid glycoside with its 6‐keto C(4) nonsubstituted aglycone.     

Three New Terpenoids from Pinus yunnanensis

A new abietatrienoid, 15‐methoxydidehydroabietic acid ( 1 ), a new ring B‐seco abietatrienoid, 10‐hydroxy‐9,10‐secoabieta‐8,11,13‐trien‐18‐oic acid ( 2 ), and a new tetracyclic triterpenoid, pinusyunnanol ( 3 ), together with five known compounds, were obtained from the twigs and needles of Pinus yunnanensis. The structures of the new compounds were elucidated by means of extensive spectroscopic analyses.     

N‐Isobutylamides and Butyrolactone from the Fruits of Zanthoxylum integrifoliolum

Further investigations of the CHCl₃‐soluble fraction of the fruit of Zanthoxylum integrifoliolum led to the isolation of three new N‐isobutylamides: lanyuamide IV ( 1 ), lanyuamide V ( 2 ), and lanyuamide VI ( 3 ), along with lanyulactone ( 4 ), a new butyrolactone derivative. The structures of these new compounds were elucidated by spectroscopic data.     

Alkaloids from the Roots of Stemona cochinchinensis

Phytochemical investigation of the roots of Stemona cochinchinensis led to the isolation and structure elucidation of a new pyrido[1,2‐a]azepine‐type alkaloid, stemocochinamine ( 1 ), and of four new pyrrolo[1,2‐a]azepine‐type alkaloids, bisdehydrostemocochinine ( 2 ), isobisdehydrostemocochinine ( 3 ), neostemocochinine ( 4 ), and isoneostemocochinine ( 5 ), together with six known alkaloids. Their structures were established on the basis of extensive 1D‐ and 2D‐NMR analyses in combination with HR‐MS experiments.     

Arylethyl (= Phenylethanoid) Glycosides and Oligosaccharide from the Stem of Cistanche tubulosa

Three new analogues of the arylethyl (= phenylethanoid) glycoside echinacoside ( 5 ), namely cistantubulosides A ( 1 ), B₁/B₂ ( 2a / 2b ), and C₁/C₂ ( 3a / 3b ), and one new oligosaccharide, cistantubulose A₁/A₂ ( 4a / 4b ), were isolated from the stems of Cistanche tubulosa (Schenk ) R. Wight , together with five known compounds, i.e., campneoside I, campneoside II ( 6 ), echinacoside ( 5 ), tubuloside, and cistanoside F. Among the compounds isolated, 2a / 2b, 3a / 3b, 4a / 4b , campneoside I, campneoside II ( 6 ), and cistanoside F each consisted of a pair of epimers. The structures of the new compounds were elucidated on the basis of spectral data.     

Sesterterpenes and 2H‐Pyran‐2‐ones (=α‐Pyrones) from the Mangrove‐Derived Endophytic Fungus Fusarium proliferatum MA‐84

Two new tricyclic sesterterpenes, fusaprolifins A and B ( 1 and 2 ), and three new 2H‐pyran‐2‐one derivatives, prolipyrones A – C ( 3 – 5 ), were isolated and characterized from Fusarium proliferatum MA‐84, an endophytic fungus obtained from the fresh tissue of the marine mangrove plant Bruguiera sexangula. In addition, two known sesterterpenes, terpestacin ( 6 ) and fusaproliferin ( 7 ), and one known 2H‐pyran‐2‐one derivative, gibepyrone D ( 8 ), were also identified. The structures of these compounds were elucidated by detailed spectroscopic analyses. Fusaprolifin A ( 1 ) showed moderate activity against brine shrimp (Artemia salina), with a lethality rate of 49.5% at 100 μg/ml, while fusaprolifin B ( 2 ) showed weak activity.     

A New Megastigmane Palmitate and a New Oleanane Triterpenoid from Aster yomena Makino

A new megastigmane palmitate, 9‐oxomegastigm‐5(13)‐ene‐2β‐palmitate ( 1 ), and a new oleanane triterpenoid, (3β)‐3,23,28‐trihydroxyolean‐12‐en‐11‐one ( 2 ), together with three known oleanane‐type triterpenoids, β‐amyrin ( 3 ), erythrodiol ( 4 ), and (3β)‐olean‐12‐ene‐3,23,28‐triol ( 5 ), were isolated from the aerial parts of Aster yomena (Asteraceae). Their structures were identified based on 1D‐ and 2D‐NMR analysis, including ¹H,¹H‐COSY, HSQC, HMBC, and NOESY techniques.     

Highly Conjugated Ergostane‐Type Steroids and Aranotin‐Type Diketopiperazines from the Fungus Aspergillus terreus BCC 4651

Two new ergostane derivatives, 12β,15α,25,26‐tetrahydroxyergosta‐4,6,8(14),22‐tetraen‐3‐one ( 1 ) and 12β,15α,25,28‐tetrahydroxyergosta‐4,6,8(14),22‐tetraen‐3‐one ( 2 ), and a new aranotin‐type diketopiperazine, bisdethiobis(methylsulfanyl)apoaranotin ( 3 ), were isolated from the fungus Aspergillus terreus BCC 4651. The structures of the new compounds were elucidated by means of NMR spectroscopic and MS analyses.     

Cytotoxic Constituents of Piper sintenense

A new pyridone alkaloid, 5,6‐dihydro‐5‐hydroxy‐1H‐pyridin‐2‐one ( 1 ), and a new ester, sintenin (=3‐(3,4‐dimethoxyphenyl)propyl 3‐(3,4‐dimethoxyphenyl)propanoate 2 ), together with three known compounds, 5,6‐dihydro‐1H‐pyridin‐2‐one ( 3 ), d‐sesamin (=5,5′‐(3a,4,6,6a‐tetrahydro‐1H,3H‐furo[3,4‐c]furan‐1,4‐diyl)bis[1,3‐benzodioxole]; 4 ), and (E)‐phytol (=3,7,11,15‐tetramethylhexadec‐2‐en‐1‐ol; 5 ) have been isolated from the whole plant of Piper sintenense. The structures of the two new compounds were determined through spectral analyses. Among twenty isolates obtained so far, four compounds exhibited effective cytotoxicities against P‐388, HT‐29, or A549 cell lines in vitro.     

Phenyl and Phenylethyl Glycosides from Picrorhiza scrophulariiflora

Three new phenyl glycosides, scrophenoside A ( 1 ), B ( 2 ), and C ( 3 ), and two new phenylethyl glycosides, scroside D ( 4 ) and scroside E ( 5 ), were isolated from the stem of Picrorhiza scrophulariiflora Pennell (Scrophularlaceae), besides five known compounds. On the basis of spectroscopic evidence, the structures of the new compounds were elucidated as 4‐acetyl‐2‐methoxyphenyl 6‐O‐[4‐(β‐D ‐glucopyranosyloxy)vanilloyl]‐β‐D ‐glucopyranoside ( 1 ), 4‐acetylphenyl 6‐O‐[(E)‐p‐coumaroyl]‐β‐D ‐glucopyranoside ( 2 ), 4‐[(1R)‐ and (1S)‐1‐hydroxyethyl]‐2‐methoxyphenyl β‐D ‐glucopyranoside ( 3a and 3b , resp.), 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐4‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 4 ), and 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐6‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 5 ).     

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.     

Phenolic and Triterpenoid Glycosides from Pyrola calliantha

Pyrocallianthasides A ( 1 ) and B ( 2 ), a new dimer and a new mono‐deglucosyl trimer of homoarbutin (=4‐hydroxy‐3‐methylphenyl β‐glucopyranoside), and callianthaside A ( 3 ), a new ursane‐type triterpene glycoside, together with three known phenolic glycosides and three known ursane‐type triterpenoids, were isolated from the whole plants of Pyrola calliantha. The structures of 1 – 3 were elucidated by chemical and spectroscopic methods.     

Heteroclitins N – Q,New Compounds from Stems of Kadsura heteroclita (Roxb.) Craib

From the stems of Kadsura heteroclita (Roxb .) Craib , a new novel C₁₉ homolignan, heteroclitin N ( 1 ), as well as three new lignans, heteroclitins O? Q ( 2 – 4 ), were isolated. Their structures were elucidated based on spectral analysis, including 1D and 2D NMR experiments. There is an additional spirocyclic oxirane system in heteroclitin O ( 2 ), which is the first example of a lignan with an oxirane ring in a spirobenzofuranoid dibenzocyclooctene structure in the genus Kadsura.     

Two New Iridoids from the Stem of Catalpa ovata

Two new iridoids, 6‐O‐[(E)‐feruloyl]jioglutin D ( 1 ) and 6‐O‐(4‐hydroxybenzoyl)jioglutin D ( 2 ), and six known compounds, minecoside ( 3 ), specioside ( 4 ), picroside II ( 5 ), picroside III ( 6 ), 4‐hydroxybenzoic acid ( 7 ), and martynoside ( 8 ), were isolated from the stem of Catalpa ovata. The structures of the new compounds were established on the basis of spectroscopic techniques, including 1D‐ and 2D‐NMR.