Petrorhagiosides A – D,New γ‐Pyrone Derivatives from Petrorhagia saxifraga Link

Four novel γ‐pyrone (=4H‐pyran‐4‐one) metabolites, petrorhagiosides A–D, along with four known analogs, have been isolated from the MeOH extract of Petrorhagia saxifraga, a perennial herbaceous plant typical of Mediterranean vegetation. The structures of the new compounds were established on the basis of extensive spectroscopic analyses including 1D‐ an 2D‐NMR (¹H,¹H‐DQ‐COSY, TOCSY, HSQC, CIGAR‐HMBC, and HSQC‐TOCSY) experiments.     

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.     

Unusual Nortriterpenoid Saponins from Stauntonia chinensis

Four new saponins, yemuosides YM₁₇–YM₂₀ ( 1 – 4 , resp.), were isolated from the rattan of Stauntonia chinensis DC. (Lardizabalaceae) along with a known saponin, nipponoside D ( 5 ). Their structures were elucidated by spectroscopic analysis and chemical evidence as 20,30‐dihydroxy‐29‐noroleanolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 1 ), 20,29‐dihydroxy‐30‐noroleanolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 2 ), 29‐hydroxy‐30‐norolean‐20(21)‐enolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 3 ), 29‐hydroxyoleanolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 4 ), and 23,29‐dihydroxyoleanolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 5 ). Yemuoside YM₁₇–YM₁₉ ( 1 – 3 , resp.) contain novel unusual nortriterpene aglycones.     

New Furostanol Glycosides from the Roots of Digitalis ciliata Trautv.

Three new furostanol glycosides, named ciliatasides A, B, and C ( 1 – 3 , resp.), have been isolated from the roots of Digitalis ciliata, along with two known furostanol glycosides. The structures of the new compounds were identified as (2α,3β,5α,14β,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐2‐hydroxyfurost‐20(22)‐en‐3‐yl β‐D ‐glucopyranosyl‐(1→2)‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranoside ( 1 ), (2α,3β,5α,14β,22R)‐26‐(β‐D ‐glucopyranosyloxy)‐2‐hydroxy‐22‐methoxyfurost‐25(27)‐en‐3‐yl β‐D ‐galactopyranosyl‐(1→2)‐[β‐D ‐xylopyranosyl‐(1→3)]‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 2 ), and (2α,3β,5α,14β,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐2,22‐dihydroxyfurostan‐3‐yl β‐D ‐glucopyranosyl‐(1→2)‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranoside ( 3 ).     

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.     

Phenolic Glycosides from the Chinese Liverwort Reboulia hemisphaerica

Four new phenolic glycosides, named rebouosides A–D ( 1 – 4 , resp.), along with three known ones 2‐(3,4‐dihydroxyphenyl)ethyl 2‐O‐α‐L ‐rhamnopyranosyl‐β‐D ‐allopyranoside ( 5 ), 2‐(3,4‐dihydroxyphenyl)ethyl β‐D ‐allopyranoside ( 6 ), 2‐(3,4‐dihydroxyphenyl)ethyl β‐D ‐glucopyranoside ( 7 ), and a nucleoside, inosine ( 8 ), were isolated from Chinese liverwort Reboulia hemisphaerica. Their structures were elucidated by acidic hydrolysis and extensive spectroscopic methods, including 2D‐NMR techniques.     

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 ).     

Phenylpropanoid Esters of Rhamnose from Buddleja asiatica

Four new phenylpropanoid esters of rhamnose, asiatisides A–D, along with the known compounds, buergeriside C₁ ( 5 ), p‐methoxycinnamic acid, ferulic acid, and O‐methylferulic acid were obtained from the aerial parts of Buddleja asiatica Lour by chromatographic methods. The new compounds were elucidated as 3‐O‐acetyl‐4‐O‐(p‐methoxycinnamoyl)‐α‐L ‐rhamnopyranose ( 1 ), 3‐O‐acetyl‐4‐O‐feruloyl‐α‐L ‐rhamnopyranose ( 2 ), 2‐O‐acetyl‐4‐O‐(O‐methylferuloyl)‐α‐L ‐rhamnopyranose ( 3 ), 2‐O‐acetyl‐4‐O‐(p‐methoxycinnamoyl)‐α‐L ‐rhamnopyranose ( 4 ) by spectral data (1D‐, 2D‐NMR, and MS), respectively.     

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.     

Itosides A – I,New Phenolic Glycosides from Itoa orientalis

Eight new benzoylated gentisyl alcohol (=2‐(hydroxymethyl)benzene‐1,4‐diol) glucosides, itosides A–H ( 1 – 8 ), together with the new pyrocatechol (=benzene‐1,2‐diol) glycoside itoside I ( 9 ) were isolated from the bark and twigs of Itoa orientalis (Flacourtiaceae). In itosides B–D ( 2 – 4 ), the gentisyl alcohol moiety was esterified by 1‐hydroxy‐6‐oxocyclohex‐2‐ene‐1‐carboxylic acid, while itosides E–H ( 5 – 8 ) contained instead an additional 2‐hydroxybenzoic acid moiety. The compounds were accompanied by the known derivatives 4‐hydroxytremulacin ( 10 ), poliothyrsoside ( 11 ), poliothyrsin ( 12 ), homaloside D ( 13 ), tremulacin, and pyrocatechol β‐D ‐glucopyranoside. The structures of the new compounds were elucidated by spectral and chemical methods.     

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 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.     

Two New Homo‐aro‐cholestane Glycosides and a New Cholestane Glycoside from the Roots and Rhizomes of Paris polyphylla var. pseudothibetica

Two new homo‐aro‐cholestane glycosides and a new cholestane glycoside, along with three known saponins, were isolated from the 95% EtOH extract of the roots and rhizomes of Paris polyphylla var. pseudothibetica. The structures of the new compounds were elucidated as 3β‐O‐{α‐L ‐rhamnopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→4)‐[α‐L ‐rhamnopyranosyl‐(1→2)]}‐β‐D ‐glucopyranosylhomo‐aro‐cholest‐5‐ene‐26‐O‐β‐D ‐glucopyranoside (parispseudoside A, 1 ), 3β‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucopyranosylhomo‐aro‐cholest‐5‐ene‐26‐O‐β‐D ‐glucopyranoside (parispseudoside B, 2 ), and (25R)‐3β‐O‐{α‐L ‐rhamnopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→4)‐[α‐L ‐rhamnopyranosyl‐(1→2)]}‐β‐D ‐glucopyranosyl‐cholesta‐5,17(20)‐diene‐16,22‐dione‐26‐O‐β‐D ‐glucopyranoside (parispseudoside C, 3 ) by spectroscopic methods, including 1D‐ and 2D‐NMR, and MS experiments, as well as chemical evidences.     

Three New Diterpenoids from Isodon nervosus

Three new ent‐kaurane diterpenoids, rabdonervosins D–F ( 1 – 3 ), were isolated from the leaves and stems of Isodon nervosus. Their structures were elucidated on the basis of spectroscopic methods including 1D‐ and 2D‐NMR analyses. Compounds 1 – 3 were evaluated for their cytotoxicity against HepG2, CNE2, PC‐9/ZD, HeLa, MCF‐7, and HCT116 cell lines. No compounds exhibited potent cytotoxicity.     

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.     

Furostane‐Type Steroidal Saponins from the Roots of Chlorophytum borivilianum

Four new furostanol steroid saponins, borivilianosides A–D ( 1 – 4 , resp.), corresponding to (3β,5α,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐22‐hydroxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐galactopyranoside ( 1 ), (3β,5α,22R,25R)‐ 26‐(β‐D ‐glucopyranosyloxy)‐22‐methoxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐galactopyranoside ( 2 ), (3β,5α,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐22‐methoxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐[β‐D ‐glucopyranosyl‐(1→2)]‐O‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 3 ), and (3β,5α,25R)‐26‐(β‐D ‐glucopyranosyloxy)furost‐20(22)‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐[β‐D ‐glucopyranosyl‐(1→2)]‐O‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 4 ), together with the known tribuluside A and (3β,5α,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐22‐methoxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→2)‐O‐[β‐D ‐xylopyranosyl‐(1→3)]‐O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐galactopyranoside were isolated from the dried roots of Chlorophytum borivilianum Sant and Fern . Their structures were elucidated by 2D ‐NMR analyses (COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry.     

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 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.     

Three New Phenol Compounds from Iris dichotoma Pall.

Three new phenolic compounds, irisdichototins D, E, and F ( 1 – 3 , resp.) were isolated from the stems of Iris dichotoma. The structures of the new compounds were elucidated by spectroscopic analyses, including 2D‐NMR techniques.     

Five New Tetranortriterpenoids from the Seeds of Toona ciliata

Five new tetranortriterpenoids, toonaciliatones B–F ( 1 – 5 , resp.), together with four known compounds, dihydrocedrelone ( 6 ), cedrelone ( 7 ), 6α‐acetoxyazadirone ( 8 ), and 6α‐acetoxy‐14β,15β‐epoxyazadirone ( 9 ), were isolated from the seeds of Toona ciliata. Their structures were elucidated by spectroscopic methods, including 1D‐ and 2D‐NMR spectroscopy.