New Polyketides Isolated from Botryosphaeria australis Strain ZJ12‐1A

Four new polyketides, botryosphaerones A–D ( 1 – 4 , resp.), were obtained from the fermentation culture of Botryosphaeria australis strain ZJ12‐1A, together with four known compounds, O‐methylasparvenone ( 5 ), 6‐ethyl‐2,7‐dimethoxyjuglon ( 6 ) and its monoacetyl derivative 7 , and O‐methylaspmenone ( 8 ). Their structures were elucidated by spectroscopic analyses, including 1D‐ and 2D‐NMR experiments, and HR‐Q‐TOF mass spectrometry, and by comparison with reported data. All compounds were evaluated for their cytotoxic and antimicrobial activities in vitro. Only compounds 6 and 7 showed cytotoxic and antimicrobial activities, as already reported.     

Three New Phthalides from Gnaphalium adnatum

Three new phthalides, gnaphalides A–C ( 1 – 3 , resp.), together with three known phthalides, were isolated from the aerial part of Gnaphalium adnatum. The structures of the new compounds were elucidated as 6‐(1,1‐dimethylprop‐2‐en‐1‐yl)‐5,7‐dihydroxy‐2‐benzofuran‐1(3H)‐one ( 1 ), 5‐hydroxy‐7‐[(2‐hydroxy‐3‐methylbut‐3‐en‐1‐yl)oxy]‐2‐benzofuran‐1(3H)‐one ( 2 ), and 1,3‐dihydro‐7‐[(3‐methylbut‐2‐en‐1‐yl)oxy]‐1‐oxo‐2‐benzofuran‐5‐yl β‐D ‐glucopyranoside ( 3 ) on the basis of spectral analyses. The structure of 1 was also confirmed by X‐ray crystallographic analysis. The three known phthalides, identified as 5,7‐dihydroxyisobenzofuran‐1(3H)‐one ( 4 ), anaphatol ( 5 ), and 7‐O‐(β‐glucopyranosyl)‐5‐hydroxyisobenzofuran‐1(3H)‐one ( 6 ), were isolated from the genus Gnaphalium for the first time.     

Curcumaromins A,B, and C,Three Novel Curcuminoids from Curcuma aromatica

Three novel curcuminoids, curcumaromins A–C ( 1 – 3 , resp.), along with a known compound, longiferone B ( 4 ) were isolated from Curcuma aromatica Salisb . The structures of the new compounds were elucidated as (1E,4Z,6E)‐5‐hydroxy‐7‐{4‐hydroxy‐3‐[(1R*,6R*)‐3‐methyl‐6‐(propan‐2‐yl)cyclohex‐2‐en‐1‐yl)phenyl}‐1‐(4‐hydroxyphenyl)hepta‐1,4,6‐trien‐3‐one ( 1 ), 2,3‐dihydro‐2‐(4‐hydroxyphenyl)‐6‐[(E)‐2‐(4‐hydroxyphenyl)ethenyl]‐5‐[(1R*,6R*)‐3‐methyl‐6‐(propan‐2‐yl)cyclohex‐2‐en‐1‐yl]‐4H‐pyran‐4‐one ( 2 ), and (1E,6E)‐1,7‐bis(4‐hydroxyphenyl)‐4‐[(1R*,6R*)‐3‐methyl‐6‐(propan‐2‐yl)cyclohex‐2‐en‐1‐yl]hepta‐1,6‐diene‐3,5‐dione ( 3 ) on the basis of spectroscopic analysis. Curcumaromins A–C ( 1 – 3 ) represented the first examples of menthane monoterpene‐coupled curcuminoids. The known compound, longiferone B ( 4 ), was the first daucane sesquiterpene isolated from the genus Curcuma.     

Four New Nortriterpenoids from Schisandra lancifolia

Four new highly oxygenated nortriterpenoids, lancifodilactones O–R ( 1 – 4 ), together with six known ones, i.e., 5 – 10 , were isolated from the leaves and stems of Schisandra lancifolia. Their structures were elucidated by spectroscopic analyses, including 1D‐ and 2D‐NMR experiments and mass spectrometry. Compounds 1 – 3 were evaluated for their cytotoxicity against NB4, A549, SHSY5Y, PC‐3, and MCF‐7 cell lines. No compounds exhibited significant cytotoxicity, the IC₅₀ values being above 50 μM .     

Three New Triterpene Saponins from Hemsleya chinensis

Three new triterpenoid saponins, xuedanglycosides A–C ( 1 – 3 , resp.), along with six known ones, were isolated from the rhizomes of Hemsleya chinensis. By detailed analysis of the NMR spectra, by chemical methods, and by comparison with spectral data of known compounds, the structures of new compounds were determined to be 16α,23α‐epoxy‐2β,3α,20β‐trihydroxy‐10α,23α‐cucurbita‐5,24‐dien‐11‐on‐2‐yl β‐D ‐glucopyranoside ( 1 ), 2β,3α,16α,20β‐tetrahydroxycucurbita‐5,25‐diene‐11,22‐dion‐2‐yl β‐D ‐glucopyranoside ( 2 ), and oleanolic acid 28‐O‐β‐xylopyranosyl‐(1→6)‐O‐β‐glucopyranoside ( 3 ). In addition, hemslecin A 2‐O‐β‐D ‐glucopyranoside ( 6 ), hemsamabilinin B ( 7 ), and hemslonin A ( 9 ) were obtained for the first time from this plant.     

Dapholidins A – C,New Isomeric Biisoflavonoids From Daphne oleoides

Three new isomeric biisoflavonoids, dapholidins A–C ( 1 – 3 , resp.), have been isolated from the AcOEt‐soluble fraction of the MeOH‐soluble extract of the roots of Daphne oleoides, along with the known compounds daphwazirin ( 4 ), daphnetin 8‐O‐β‐D ‐glucopyranoside ( 5 ), daphnin ( 6 ), daphneticin 4″‐O‐β‐D ‐glucopyranoside ( 7 ), and 6,7‐dihydroxy‐3‐methoxy‐8‐[2‐oxo‐2H‐1‐benzopyran‐7‐(O‐β‐D ‐glucopyranosyl)‐8‐yl]‐2H‐1‐benzopyran‐2‐one ( 8 ). The structures of the new compounds were determined by spectroscopic analyses, including 1D‐ and 2D‐NMR.     

Three New Triterpenoid Saponins from Ardisia crenata

Three new triterpenoid saponins, ardisicrenoside I ( 1 ), ardisicrenoside J ( 2 ), and ardisicrenoside M ( 3 ), along with eight known compounds, were isolated from the roots of Ardisia crenata Sims . Their structures were elucidated as 16α‐hydroxy‐30,30‐dimethoxy‐3β‐O‐{β‐D ‐xylopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl‐(1→4)‐[β‐D ‐glucopyranosyl‐(1→2)]‐α‐L ‐arabinopyranosyl}‐13β,28‐epoxyoleanane ( 1 ), 16α‐hydroxy‐30,30‐dimethoxy‐3β‐O‐{α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl‐(1→4)‐[β‐D ‐glucopyranosyl‐(1→2)]‐α‐L ‐arabinopyranosyl}‐13β,28‐epoxyoleanane ( 2 ), 30,30‐dimethoxy‐16‐oxo‐3β‐O‐{β‐D ‐xylopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl‐(1→4)‐[β‐D ‐glucopyranosyl‐(1→2)]‐α‐L ‐arabinopyranosyl}‐13β,28‐epoxyoleanane ( 3 ), ardisiacrispin A ( 4 ), ardisiacrispin B ( 5 ), ardisicrenoside B ( 6 ), ardisicrenoside A ( 7 ), ardisicrenoside H ( 8 ), ardisicrenoside G ( 9 ), cyclamiretin A‐3β‐O‐β‐D ‐xylopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐arabinopyranoside ( 10 ), and cyclamiretin A‐3β‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐arabinopyranoside ( 11 ) by means of chemical and spectral analysis, and their cytotoxicities were evaluated in vitro.     

Glycopentosides D – F,Three New Phenolic Glycosides from Glycosmis pentaphylla

A phytochemical investigation of the BuOH‐soluble fraction of the EtOH extract from the stems of Glycosmis pentaphylla resulted in the isolation of three new phenolic glycosides, glycopentosides D–F ( 1 – 3 , resp.). Their structures were determined by using spectroscopic analysis including UV, ¹H‐ and ¹³C‐NMR, DEPT, COSY, ROESY, HMBC, HSQC, HR‐ESI‐MS, and acid hydrolysis.     

Clerodane and ent‐Kaurane Diterpene Glycosyl and Glycoside Derivatives from the Leaves of Casearia sylvestris

Five new clerodane diterpene glycosyl derivatives, caseariasides A–E ( 1 – 5 , resp.) and three new ent‐kaurane diterpene glucosides, sylvestrisides C–E ( 6 – 8 , resp.) were isolated from the leaves of Casearia sylvestris. Their structures were determined on the basis of chemical and spectroscopic analyses.     

Nine New Sesquiterpenes from Dendrobium nobile

Nine new sesquiterpenes, i.e., dendronobilins A–I ( 1 – 9 ), with copacamphane‐type ( 1 ), picrotoxane‐type ( 2 – 6 ), muurolene‐type ( 7 ), alloaromadendrane‐type ( 8 ), and cyclocopacamphane‐type ( 9 ) skeletons, were isolated from the 60% EtOH extract of the stems of Dendrobium nobile. Their structures were established as (1R,2R,4S,5S,6S,8S,9R)‐2,8‐dihydroxycopacamphan‐15‐one ( 1 ), (2β,3β,4β,5β)‐2,4,11‐trihydroxypicrotoxano‐3(15)‐lactone ( 2 ), (2β,3β,5β,9α,11β)‐2,11‐epoxy‐9,11,13‐trihydroxypicrotoxano‐3(15)‐lactone ( 3 ), (2β,3β,5β,12R*)‐2,11,13‐trihydroxypicrotoxano‐3(15)‐lactone ( 4 ), (2β,3β,5β,12S*)‐2,11,13‐trihydroxypicrotoxano‐3(15)‐lactone ( 5 ), (2β,3β,5β,9α)‐9,10‐cyclo‐2,11,13‐trihydroxypicrotoxano‐3(15)‐lactone ( 6 ), (9β,10α)‐muurol‐4‐ene‐9,10,11‐triol ( 7 ), (10α)‐alloaromadendrane‐10,12,14‐triol ( 8 ), and (5β)‐cyclocopacamphane‐5,12,15‐triol ( 9 ) on the basis of spectroscopic analysis. The absolute configuration of compound 1 was tentatively assigned as (1R,2R,4S,5S,6S,8S,9R) according to its CD spectrum and the octant rule. Compounds 1 and 4 – 9 were inactive in our preliminary in vitro immunomodulatory bioassay.     

Prenylated Benzene Metabolites from Melicope pteleifolia

Chemical investigation on the stem and root of Melicope pteleifolia afforded three new prenylated benzene metabolites as racemic mixtures, named pteleifolins A–C ( 1 – 3 , resp.). Their gross structures were elucidated on the basis of spectroscopic analysis, especially 2D‐NMR experiments. An enantiomer resolution of (±)‐ 1 using chiral HPLC was performed, and the absolute configuration of the enantiomers were determined to be (+)‐(S)‐ 1 and (?)‐(R)‐ 1 by means of circular‐dichroism analysis.     

Neolignans from the Leaves of Casearia sylvestris Swartz

Six new neolignans, casearialignans A–F ( 1 – 6 , resp.) and one known lignan syringaresinol‐β‐D ‐glucoside were isolated from the leaves of Casearia sylvestris. Their structures were determined on the basis of 1D‐ and 2D‐NMR, and HR‐ESI‐MS analyses. The relative and absolute configurations were determined by the value of the coupling constants and CD spectral analysis, respectively.     

New Alkaloids from Aconitum vaginatum

Two new amide alkaloids, vaginatunine A and B ( 1 and 2 , resp.), and a new C₁₈‐diterpenoid alkaloid vaginatunine C ( 3 ), together with four known alkaloids, were isolated from the tubers of Aconitum vaginatum. Their structures were determined by means of spectroscopic analyses and comparison of the data with those reported previously.     

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.     

Three New Lanostane Triterpenoids,Inonotsutriols A,B, and C,from Inonotus obliquus

Three new lanostane‐type triterpenoids, inonotsutriols A ( 1 ), B ( 2 ), and C ( 3 ) were isolated from the sclerotia of Inonotus obliquus (Pers .: Fr.) (Japanese name: kabanoanatake; Russian name: chaga). Their structures were determined to be (3β,21R,24S)‐21,24‐cyclolanost‐8‐ene‐3,21,25‐triol ( 1 ), (3β,21R,24R)‐21,24‐cyclolanost‐8‐ene‐3,21,25‐triol ( 2 ), and (3β,21R,24S)‐21,24‐cyclolanosta‐7,9(11)‐diene‐3,21,25‐triol ( 3 ) on the basis of NMR spectroscopy including 1D and 2D experiments (¹H,¹H‐COSY, NOESY, HMQC, and HMBC) and EI‐MS.     

Meliarachins A–K: Eleven Limonoids from the Twigs and Leaves of Melia azedarach

Eleven new limonoids, meliarachins A–K ( 1 – 11 , resp.), together with five known ones, were isolated from the twigs and leaves of Melia azedarach. The structures of the new compounds were elucidated on the basis of spectroscopic analysis. Compounds 4 and 8 exhibited moderate antibacterial activities against Gram‐positive bacteria.     

New Minor Spirostane Glycosides from Ypsilandra thibetica

A further phytochemical investigation on the whole plants of Ypsilandra thibetica yielded three new spirostane glycosides, named ypsilandrosides M–O ( 1 – 3 ). Their structures were established as (3β,11α,25R)‐3,11‐dihydroxyspirost‐5‐en‐12‐one 3‐{O‐α‐L ‐rhanmopyranosyl‐(1→4)‐O‐L ‐rhanmopyranosyl‐(1→4)‐O‐[α‐L ‐rhanmopyranosyl‐(1→2)]‐β‐D ‐glucopyranoside} ( 1 ), (3β,7β,25R)‐spirost‐5‐ene‐3,7‐diol 3‐{O‐α‐L ‐rhanmopyranosyl‐(1→4)‐O‐α‐L ‐rhanmopyranosyl‐(1→4)‐O‐[α‐L ‐rhanmopyranosyl‐(1→2)]‐β‐D ‐glucopyranoside} ( 2 ), and (3β,7α,25R)‐spirost‐5‐ene‐3,7,17‐triol 3‐{O‐α‐L ‐rhanmopyranosyl‐(1→4)‐O‐α‐L ‐rhanmopyranosyl‐(1→4)‐O‐[α‐L ‐rhanmopyranosyl‐(1→2)]‐β‐D ‐glucopyranoside} ( 3 ) by means of a combination of MS, 1D‐ and 2D‐NMR spectroscopic methods, and chemical degradation. Among them, compound 3 is the first pennogenin (=(3β,25R)‐spirost‐5‐ene‐3,17‐diol) saponin whose aglycone contains an OH group at C(7). Compounds 1 – 3 were evaluated for the inhibition of the growth of five tumor cell lines, but all of them proved to be inactive.     

Five New C19‐Diterpenoid Alkaloids from Aconitum hemsleyanum

Five new C₁₉‐diterpenoid alkaloids, named hemsleyaconitines A–E ( 1 – 5 , resp.), were isolated from Aconitum hemsleyanum Pritz. By UV, IR, MS, 1D‐ and 2D‐NMR analyses, their structures were elucidated as 18‐dehydroxygeniculatine D ( 1 ), 6‐hydroxy‐14‐O‐veratroylneoline ( 2 ), 14‐O‐acetyl‐8‐ethoxysachaconitine ( 3 ), 18‐veratroylkaracoline ( 4 ) and 8‐O‐ethylaustroconitine B ( 5 ).     

Three New C19‐Diterpenoid Alkaloids from Aconitum transsectum

Three new C₁₉‐diterpenoid alkaloids, named aconitramines A ( 1 ), B ( 2 ), and C ( 3 ), were isolated from Aconitum transsectum. By UV, IR, 1D‐ and 2D‐NMR, and MS analyses, their structures were elucidated as 18‐methoxyvilmoraconitine, 18‐demethoxydolichotine A, and 18‐demethoxydolichotine B. Compound 1 is the second known C₁₉‐diterpenoid alkaloid with a three‐membered ring formed by C(8), C(9), and C(10).     

Cytotoxic Diterpenes from the Root Tuber of Curcuma wenyujin

Bioassay‐guided fractionation of ethanolic extract from the root tuber of Curcuma wenyujin afforded three new diterpenes, curcumrinols A–C ( 1 – 3 ), where 2 is the (14S)‐epimer of 1 . The structures of 1 – 3 were established on the basis of spectroscopic analysis, mainly NMR and MS. 1 – 3 were tested in vitro for their cytotoxic activity against the HL‐60 and K562 cancer cells. Among the compounds tested, 1 exhibited medium cytotoxicity against K‐562 and HL60 human cancer cells with IC₅₀ values of 11.2 and 3.2 μg/ml, respectively. However, 2 showed only weak activity against the above cancers cells, which suggested that C(14) may be an important position for cytotoxic activity.