A New ent‐Kaurane Diterpene from Stems of Alibertia macrophylla K. Schum. (Rubiaceae)

Phytochemical investigations of the stems of a specimen of Alibertia macrophylla led to the isolation and characterization of the new diterpene ent‐kaurane‐2β,3α,16α‐triol ( 1 ), along with triterpenes 2 – 8 , iridoids 9 – 12 , and phenolic acids 13 – 15 . The structure of 1 was established based on spectroscopic studies (¹H‐ and ¹³C‐NMR, IR, and HR‐ESI‐MS). This is the first report of the isolation of a diterpene from the Alibertia genus in Rubiaceae.     

Flavonol Glycosides and Iridoids from Asperula lilaciflora

A new flavonol glycoside, quercetin 3‐O‐[6′′′‐O‐3,5‐dihydroxycinnamoyl‐β‐glucopyranosyl‐(1→2)]‐β‐galactopyranoside (named lilacifloroside; 1 ) and a new iridoid 2 (named asperulogenin), were isolated from the aerial parts of Asperula lilaciflora in addition to eight known secondary metabolites, i.e., quercetin, kaempferol, quercetin 3‐O‐β‐glucopyranosyl‐(1→2)‐β‐galactopyranoside, quercetin 3‐O‐β‐glucopyranosyl‐(1→2)‐arabinopyranoside, asperuloside, deacetylasperulosidic acid, asperulosidic acid methyl ester, and chlorogenic acid. The structures were elucidated on the basis of extensive 1D‐ and 2D‐NMR experiments as well as MS data. Compound 1 contains the rare 3,5‐dihydroxycinnamoyl moiety in its structure. This work constitutes the first phytochemical study of the title plant.     

Two New Kaempferol Glycosides from Androsace umbellata

Two new kaempferol glycosides, 5‐hydroxy‐2‐(4‐hydroxyphenyl)‐4‐oxo‐7‐(α‐L ‐rhamnopyranosyloxy)‐4H‐chromen‐3‐yl 2‐O‐acetyl‐3‐O‐β‐D ‐glucopyranosyl‐α‐L ‐rhamnopyranoside ( 1 ) and 5‐hydroxy‐2‐(4‐hydroxyphenyl)‐4‐oxo‐7‐(α‐L ‐rhamnopyranosyloxy)‐4H‐chromen‐3‐yl β‐D ‐glucopyranosyl‐(1→2)‐6‐O‐[(2E)‐3‐(4‐hydroxyphenyl)prop‐2‐enoyl]‐β‐D ‐glucopyranosyl‐(1→2)‐β‐D ‐glucopyranoside ( 2 ), along with ten known compounds, were isolated from the 95% EtOH extract of the whole plant of Androsace umbellata. The structures of the new glycosides were determined on the basis of detailed spectroscopic analyses, including 1D‐ and 2D‐NMR, MS, and chemical methods.     

Three New Kaempferol Glycosides from Cardamine leucantha

Three new kaempferol glycosides, kaempferol 3‐O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐galactopyranosyl‐7‐O‐α‐L ‐rhamnopyranoside ( 1 ), kaempferol 3‐O‐β‐D ‐galactopyranosyl‐7‐O‐β‐D ‐glucopyranosyl‐(1→3)‐α‐L ‐rhamnopyranoside ( 2 ), and kaempferol 3‐O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐galactopyranosyl‐7‐O‐β‐D ‐glucopyranosyl‐(1→3)‐α‐L ‐rhamnopyranoside ( 3 ), were isolated from the whole herbs of Cardamine leucantha, along with three known kaempferol glycosides, kaempferol 7‐O‐α‐L ‐rhamnopyranoside, kaempferitrin, and kaempferol 3‐O‐β‐D ‐galactopyranosyl‐7‐O‐α‐L ‐rhamnopyranoside. Their structures were elucidated on the basis of spectroscopic methods.     

Six New C21 Steroidal Glycosides from Cynanchum bungei Decne

Six new C₂₁ steroidal glycosides 1 – 6 were isolated from the stem parts of Cynanchum bungei Decne . The structures of the new glycosides were determined on the basis of spectroscopic analysis, including 1D‐ and 2D‐NMR and HR‐ESI‐MS techniques as well as by comparison of their spectral data with those of related compounds.     

Iridoid Glycosides from Lamiophlomis rotata

The seven new iridoid diglycosides 1 – 7 , together with eleven known iridoid and phenylpropanoid glycosides, were isolated from the 50% EtOH extract of the roots of Lamiophlomis rotata. Their structures were elucidated by chemical and spectroscopic methods.     

Three New C21 Steroidal Glycosides from the Stems of Marsdenia tenacissima

Three new glycosides, (3β,5α,8α,11α,12β,14β,17α,20R)‐3‐[(2,6‐dideoxy‐4‐O‐(6‐deoxy‐3‐O‐methyl‐β‐D ‐allopyranosyl)‐3‐O‐methyl‐β‐D ‐arabino‐hexopyranosyl)oxy]‐12‐O‐tigloyl‐8,20 : 11,20‐diepoxypregnane‐12,14‐diol ( 1 ), (3β,5α,8α,11α,12β,14β,17α,20R)‐3‐[(2,6‐dideoxy‐4‐O‐(6‐deoxy‐3‐O‐methyl‐β‐D ‐ allopyranosyl)‐3‐O‐methyl‐β‐D ‐arabino‐hexopyranosyl)oxy]‐12‐O‐(2‐methylbutanoyl)‐8,20 : 11,20‐diepoxypregnane‐12,14‐diol ( 2 ), and (3β,5α,11α,12β,14β,17α)‐12‐acetoxy‐3‐[(2,6‐dideoxy‐4‐O‐(6‐deoxy‐3‐O‐methyl‐β‐D ‐allopyranosyl)‐3‐O‐methyl‐β‐D ‐arabino‐hexopyranosyl)oxy]‐20‐oxo‐8,14‐epoxypregnan‐ 11‐yl isobutyrate ( 3 ) were isolated from the stems of Marsdenia tenacissima. The structures of the new compounds were elucidated by means of spectral data, including HR‐ESI‐MS, and 1D‐ and 2D‐NMR.     

Two New Phenylethanoid Glycosides from Callicarpa longissima

Two new phenylethanoid glycosides, longissimosides A and B ( 1 and 2 , resp.), together with eight structurally related known compounds, were isolated from the EtOH extract of leaves and stems of Callicarpa longissima (Hemsl .) Merr . The structures of 1 and 2 were elucidated as 2‐(3,4‐dihydroxyphenyl)ethyl O‐(α‐L ‐rhamnopyranosyl)‐(1→3)‐O‐(2‐O‐syringoyl‐β‐D ‐xylopyranosyl)‐(1→6)‐ 4‐O‐[(E)‐caffeoyl]‐β‐D ‐glucopyranoside ( 1 ) and 2‐(3‐hydroxy‐4‐methoxyphenyl)ethyl O‐(α‐L ‐rhamnopyranosyl)‐(1→3)‐O‐(β‐D ‐apiofuranosyl)‐(1→6)‐4‐O‐[(E)‐isoferuloyl]‐β‐D ‐glucopyranoside ( 2 ) on the basis of spectroscopic data and acid hydrolysis.     

Two New Secoiridoid Glycosides from Tripterospermum chinense

Two new secoiridoid glycosides, tripterospermumcin A ( 1 ) and B ( 2 ), were isolated from the EtOH extract of the aerial parts of Tripterospermum chinense (Migo ) H. Smith , along with three known compounds, secologanin, secologanol, and sweroside. Their structures were established on the basis of UV, IR, MS, and extensive 1D‐ and 2D‐NMR analyses, as well as by literature comparison of spectroscopic data.     

Triterpenoids and Iridoid Glycosides from Gentiana dahurica

One new and six known pentacyclic triterpenoids, 1 and 4 – 9 , resp., along with two new and three known iridoid glycosides, 2 and 3 , and 10 – 12 , resp., were isolated from the roots of Gentiana dahurica (‘Qin‐Jiao’). The new structures were elucidated by means of spectroscopic and chemical methods as 1β,2α,3α,24‐tetrahydroxyursa‐12,20(30)‐dien‐28‐oic acid ( 1 ), 6′‐O‐acetylgentiopicroside ( 2 ), and 3′‐acetylgentiopicroside ( 3 ). Isolated compounds were tested for their cytotoxicity against the MCF‐7 human breast cancer cell line using the MTT assay. Among them, triterpenoids 2α,3β,24‐trihydroxyurs‐12‐en‐28‐oic acid ( 6 ) and 3β,24‐dihydroxyurs‐12‐en‐28‐oic acid ( 9 ) were found to have moderate cytotoxic effects with IC₅₀ values of 20.9 and 21.7 μg/ml, respectively. Additionally, the chemotaxonomic significance of the identified secondary metabolites is briefly discussed.     

Iridoid Glycosides from Gardenia jasminoides Ellis

Three new iridoid glycosides, 4″‐O‐[(E)‐p‐coumaroyl]gentiobiosylgenipin ( 1 ), 6′‐O‐[(E)‐caffeoyl]deacetylasperulosidic acid methyl ester ( 2 ), and 6′‐O‐[(E)‐sinapoyl]gardoside ( 3 ), together with seven analogues, 4 – 10 , were isolated from the BuOH extract of the fruits of Gardenia jasminoides Ellis . Their structures were determined by means of spectroscopic analyses, including HR‐ESI‐MS, IR, and ¹H‐ and ¹³C‐NMR, and 2D experiments (COSY, HSQC, and HMBC), and comparison with known related compounds.     

Three New Cycloartane (=9,19‐Cyclolanostane) Glycosides from Cimicifuga foetida

Three new cycloartane glycosides, 24‐epicimigenol 3‐(α‐L ‐arabinopyranoside) ( 1 ), (3β,16β)‐cycloartane‐3,16,22,24,25‐pentol 3‐(β‐D ‐xylopyranoside) ( 2 ), and (3β,15α,16β)‐cycloartane‐3,15,16,24,25‐pentol 3‐(β‐D ‐xylopyranoside) ( 3 ), together with five known compounds, including four cycloartane glycosides and bergenin, were isolated from the rhizomes of Cimicifuga foetida. Their structures were elucidated by spectroscopic methods.     

A New Megastigmane Glucoside and Three New Flavonoid Glycosides from Spiraea prunifolia var. simpliciflora

A new megastigmane glucoside, simplicifloranoside ( 1 ), and three new flavonol glycosides, prunifolianosides A–C ( 2 – 4 , resp.), were isolated from the aerial parts of Spiraea prunifolia var. simpliciflora. In addition, fifteen known compounds, including five phenolic acids, three lignans, four flavonoids, one eugenol glycoside, and two alkyl‐primeverosides, were also identified. Their structures were elucidated on the basis of detailed spectroscopic analyses and acid hydrolysis.     

Two New C21 Steroidal Glycosides from the Stems of Marsdenia tenacissima

Two new pregnane glycosides, (3β,5α,12β,14β,17α)‐3‐(β‐cymaropyranosyloxy)‐8,14,17,20‐tetrahydroxypregnan‐12‐yl benzoate ( 1 ) and (3β,5α,12β,14β,17α)‐3‐(β‐cymaropyranosyloxy)‐8,14,17,20‐tetrahydroxypregnan‐12‐yl cinnamate ( 2 ) were isolated from the stems of Marsdenia tenacissima. The structures and relative configurations of the new compounds were elucidated by spectroscopic methods, including mass spectrometry and NMR spectroscopy.     

A New Cardenolide and Two New Pregnane Glycosides from the Root Barks of Periploca sepium

A new cardenolide and two new pregnane glycosides, periplogenin 3‐[O‐β‐glucopyranosyl‐(1→4)‐β‐sarmentopyranoside] ( 1 ), (3β,20S)‐pregn‐5‐ene‐3,17,20‐triol 20‐[O‐β‐glucopyranosyl‐(1→6)‐O‐glucopyranosyl‐(1→4)‐β‐canaropyranoside] ( 2 ), and (3β,14β,17α)‐3,14,17‐trihydroxy‐21‐methoxypregn‐5‐en‐20‐one 3‐[O‐β‐oleandropyranosyl‐(1→4)‐O‐β‐cymaropyranosyl‐(1→4)‐β‐cymaropyranoside] ( 3 ), were isolated from the root barks of Periploca sepium Bge , together with seven related known compounds, periplogenin, xysmalogenin, (3β,20S)‐pregn‐5‐ene‐3,17,20‐triol, (3β,14β,17α)‐3,14,17‐trihydroxy‐21‐methoxypregn‐5‐en‐20‐one, (3β,20S)‐pregn‐5‐ene‐3,20‐diol 3‐β‐glucopyranoside 20‐β‐glucopyranoside, (3β,20S)‐pregn‐5‐ene‐3,20‐diol 3‐[O‐2‐O‐acetyl‐β‐digitalopyranosyl‐(1→4)‐β‐cymaropyranoside] 20‐[O‐β‐glucopyranosyl‐(1→6)‐O‐β‐glucopyranosyl‐(1→2)‐β‐digitalopyranoside], and (3β,20S)‐ pregn‐5‐ene‐3,20‐diol 20‐[O‐β‐glucopyranosyl‐(1→6)‐β‐glucopyranoside]. Their structures were elucidated on the basis of spectroscopic analyses.     

Five New Flavonol Glycosides from the Fresh Flowers of Camellia reticulata

Thirty‐one phenolic constituents, including 13 flavonol glycosides, 3 dihydroflavonols, 5 flavan‐3‐ols, 4 hydrolyzable tannins, and 6 phenylpropanoids, were isolated from the fresh flowers of Camellia reticulata for the first time. Five of them are new flavonol glycosides. Their structures were elucidated by detailed spectroscopic analyses.