Two new epoxysteroids from Helianthus tuberosus

Two new epoxy steroids, 5α,8α-epidioxy-22β,23β-epoxyergosta-6-en-3β-ol (1) and 5α,8α-epidioxy-22α,23α-epoxyergosta-6-en-3β-ol (2), and ten known steroids including (24R)-5α,8α-epidioxyergosta-6-en-3β-ol (3), (22E,24R)-5α,8α-epidioxyergosta-6,22-dien-3β-ol (4), (22E,24R)-5α,8α-epidioxyergosta-6,9(11),22-trien-3β-ol (5), β-sitosterol (6), sitost-5-en-3β-ol acetate (7), 7α-hydroxysitosterol (8), schleicheol 2 (9), (24R)-24-ethyl-5α-cholestane-3β,5α,6β-triol (10), 7α-hydroxystigmasterol (11), and stigmasterol (12) were isolated from Helianthus tuberosus grown in Laizhou salinized land of coastal zone of Bohai Sea, China. The structures of these compounds were unambiguously established by 1D, 2D NMR and mass spectroscopic techniques. The new compounds 1 and 2 exhibited weak antibacterial activity and no antifungal activity.     

A New Xanthanolide from Carpesium longifolium

A new xanthanolide was isolated from the aerial parts of Carpesium longifolium.It‘‘‘‘‘‘‘‘s structure was elucidated as 1β,4β-epoxy-5β-hydroxy-10αH-xantha-11(13)-3n-12,8β-olide by spectral methods(HRMS,1D and 2D NMR).     

Four new eremophilendiolides from Ligularia atroviolacea

From Ligularia atroviolacea, four new eremophilendiolides, 81$-hydroxy-eremophil-3,7 （11）-dien-12,8α（14,6α）-diolide （1）, 8β-methoxy-eremophil-3,7（11）-dien-12,8α（14,6α）-diolide （2）, 8α-hydroxy-eremophil-3,7（11）-dien-12,8lβ（14,6α）-diolide （3） and eremophil-3,7（11）,8-trien-12,8 （14,6α）-diolide （4）, as well as a known diolide （5） were isolated. Their structures were elucidated on the basis of 1D and 2D NMR as well as ESI-MS spectral data.     

Structure of a new sterol from the South China sponge Dysidea fragilis

A new sterol, 5a-cholesta-8(14),24(25)-diene-3/β, 6a-diol (1) and a known sterol (24Z)-24-ethyl-cholesta-7(8),24(28)-diene-3β,5a,6β-triol (2) have been isolated from the South China Seasponge Dysidea fragilis. The structure and relative stereochemistry of 1 were established by spectralanalysis, including 2D NMR experiments.     

Three new steroidal glycosides from the roots of Cynanchum auriculatum

Three new steroidal glycosides, cyanoauriculosides F, G and H (1-3), were isolated from the roots of Cynanchum auriculatum (Asclepiadaceae) along with two known steroidal derivatives. On the basis of spectroscopic analysis and chemical methods, their structures were identified as 20-O-acetyl-8,14-seco-penupogenin-8-one 3-O-α-L-cymaropyranosyl-(1→4)-β-D-cymaropyranosyl-(1→4)-α-L-diginopyranosyl-(1→4)-β-D-cymaropyranoside (1), 2',3'-Z-gagaminine 3-O-α-L-cymaropyranosyl-(1→4)-β-D-cymaro-pyranosyl-(1→4)-α-L-diginopyranosyl-(1→4)-β-D-cymaropyranoside (2), 17-O-acetyl-kidjoranin 3-O-α-L-cymaropyranosyl-(1→4)-β-D-cymaropyranosyl-(1→4)-α-L-cymaro-pyranosyl-(1→4)-β-D-digitoxopyranosyl-(1→4)-β-D-digitoxopyranoside (3), gagaminine 3-O-α-L-cymaropyranosyl-(1→4)-β-D-cymaropyranosyl-(1→4)-α-L-digino-pyranosyl-(1→4)-β-D-cymaropyranoside (4) and wilfoside D1N (5).     

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.     

New Eremophilenolactones from Senecio nemorensis

Three new eremophilane sesquiterpenes were isolated from the MeOH extract of the roots of Senecio nemorensis. Their structures were identified as 8α‐hydroxy‐6β‐(isobutanoyloxy)‐1‐oxoeremophila‐7(11),9‐dieno‐12,8β‐lactone ( 1 ), 6β,8β‐dimethoxy‐1‐oxoeremophila‐7(11),9‐dieno‐12,8α‐lactone ( 2 ), and 10α‐hydroxy‐6β‐(isobutanoyloxy)‐1‐oxoeremophila‐7(11),8‐dieno‐12,8‐lactone ( 3 ), respectively, based on spectroscopic data, including IR, EI‐MS, HR‐ESI‐MS, and 1D‐ and 2D‐NMR data.     

Three steroids with unique structural feature of 5β-Spirostan-1β,3β,17α-trihydroxyl from Reineckia carnea

A new spirostanol sapogenin and two spirostanol saponins, tentatively named reineckiagenin A (1), reineckiagenoside A (2), and reineckiagenoside B (3), were isolated from the whole plant of Reineckia carnea. By detailed analysis of their 1D and 2D NMR spectra, chemical methods, and by comparison with spectra data of known compounds, the structures of the new steroids were determined to be 25(S)-5β-spirostan-1β,3β,17α-triol (1), 25(S)-5β-spirostan-1β,3β,17α-triol 1-O-β-D-xylopyranoside (2), 25(S)-5β-spirostan-1β,3β,17α-triol 1-O-α-L-rhamnopyranosyl-(1→2)-β-D-xylopyranoside (3). Compounds 1, 2, and 3 are the first naturally occurring steroids with unique structural feature of 5β-spirostan-1β,3β,17α-trihydroxyl.     

Structural determination of two new triterpenoid saponins acylated with monoterpenic acid from Gymnocladus chinensis Baill

Two new triterpenoid saponins acylated with monoterpenic acid, 2β,23-dihydroxy-3-O-α-L-rhamnopyranosyl-21-O-{(6S)-2-trans-2,6-dimethyl-6-O-[3-O-(β-D-glucopyranosyl)-4-O-(2-methylbutanoyl)-β-L-arabinopyranosyl]-2,7-octadienoyl)-acacic acid 28-O-β-D-xylopyranosyl-(1?→?3)-β-D-xylopyranosyl-(1?→?4)-[β-D-glucopyranosyl-(1?→?3)]-α-L-rhamnopyranosyl-(1?→?2)-[α-L-rhamnopyranosyl-(1?→?6)]-β-D-glucopyranosyl ester and 2β,23-dihydroxy-3-O-α-L-rhamnopyranosyl-21-O-{(6S)-2-trans-2,6-dimethyl-6-O-[4-O-((6S)-2-trans-2,6-dimethyl-6-O-(β-L-arabinopyranosyl)-2,7-octadienoyl)]-β-L-arabinopyranosyl]-2,7-octadienoyl}-acacic acid 28-O-β-D-xylopyranosyl-(1?→?3)-β-D-xylopyranosyl-(1?→?4)-[β-D-glucopyranosyl-(1?→?3)]-α-L-rhamnopyranosyl-(1?→?2)-[α-L-rhamnopyranosyl-(1?→?6)]-β-D-glucopyranosyl ester were isolated from the fruit of Gymnocladus chinensis Baill. and the structural elucidation of both the compounds was accomplished by extensive studies of their spectroscopic (1D and 2D NMR, TOF-MS, QFT-MS) and chemical methods.     

Diversity of Sesquiterpenoids from Carpesium cernuum

Two new sesquiterpene lactones, 6β‐hydroxy‐8α‐ethoxyeremophil‐7(11)‐en‐12,8β‐olide ( 1 ) and 4β,10β‐dihydroxy‐1αH,5αH,11αH‐guaian‐12,8β‐olide ( 2 ), together with 22 known sesquiterpenoids with various structural types, were isolated from Carpesium cernuum (Compositae). Their structures and configurations were elucidated by extensive 1D‐ and 2D‐NMR spectroscopic analysis in combination with MS experiments, and comparison with literature data of related compounds.     

Eremophilane‐Type Sesquiterpenes from the Roots of Ligularia virgaurea

From the roots of Ligularia virgaurea, five new eremophilane‐type sesquiterpenes were isolated, including three new eremophilenolides, 6β‐(angeloyloxy)‐1α,8β,10β‐trihydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 1 ), 6β‐(angeloyloxy)‐1β,10β‐epoxy‐8β‐ethoxyeremophil‐7(11)‐en‐12,8α‐olide ( 2 ), and 1β,10β‐epoxy‐8β‐ethoxy‐6β‐[(2‐methylacryloyl)oxy]eremophil‐7(11)‐en‐12,8α‐olide ( 3 ), two new noreremophilanes, 3β‐[(2‐methylacryloyl)oxy]‐8‐oxo‐12‐noreremophil‐6‐en‐11‐one ( 9 ), and 9β‐hydroxy‐8‐oxo‐12‐noreremophil‐6‐en‐11‐one ( 10 ), and six known eremophilanes, namely 4 – 8 , and 11 . Their structures were elucidated by means of spectral methods, such as IR, HR‐ESI‐MS, and 1D‐ and 2D‐NMR, and by comparison of the spectral data with those reported for structurally related compounds.     

Chemical Constituents from Craibiodendron yunnanense

A new triterpene, (3β,12β)‐taraxast‐20(30)‐ene‐3,12‐diol (=(3β,12β,18α,19α)‐urs‐20(30)‐ene‐3,12‐diol; 1 ), together with the known compounds ursolic acid, α‐amyrin, β‐amyrin, (2α,3β)‐2,3‐dihydroxyursa‐5,12‐dien‐28‐oic acid, (2α,3β)‐2,3,23‐trihydroxyurs‐12‐en‐28‐oic acid, (2S,3S,4R,8Z)‐1‐O‐(β‐D ‐glucopyranosyl)‐2‐{[(2R)‐2‐hydroxydocosanoyl]amino}octadec‐8‐ene‐1,3,4‐triol, and (2S,3S,4R,8Z)‐1‐O‐(β‐D ‐glucopyranosyl)‐2‐[(palmitoyl)amino]octadec‐8‐ene‐1,3,4‐triol, and quercetin 3‐(β‐D ‐glucopyranoside) were isolated from the leaves of Craibiodendron yunnanense. Their structures were established on the basis of spectral evidence. The last four compounds were identified for the first time in this plant.     

Platycoside N: a new oleanane-type triterpenoid saponin from the roots of Platycodon grandiflorum

A new oleanane-type triterpenoid saponin, named platycoside N (1), together with six known saponins, was isolated from the roots of Platycodon grandiflorum. On the basis of acid hydrolysis, comprehensive spectroscopic data analyses and comparison with the spectral data of the known compounds, its structure was elucidated as 3-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl-2β,3β,16α,23-tetrahydroxyolean-12-en-28-oic acid 28-O-β-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside. The six known compounds were platycodin D (2), deapioplatycodin D (3), platycodin D3 (4), deapioplatycodin D3 (5), platycoside E (6) and deapioplatycoside E (7).     

New Eremophilenolides from Senecio dianthus

From the aerial parts of Senecio dianthus, four new eremophilenolides ( 1 – 4 , resp.) and one new eremophilenolide alkaloid ( 5 ), of the relatively uncommon eremophilenoid‐type sesquiterpenoid lactones, were isolated together with three known sesquiterpenoid lactones, 10β‐hydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 6 ), 8β,10β‐dihydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 7 ), and 10α‐hydroxy‐1‐oxoeremophila‐7(11),8(9)‐dien‐12,8‐olide ( 8 ). On the basis of IR, MS, and NMR data, particularly 2D‐NMR analyses, the structures of the new compounds were established as: 2β‐(angeloyloxy)‐10β‐hydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 1 ), 6β‐(angeloyloxy)‐10β‐hydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 2 ), 2β‐(angeloyloxy)‐8β,10β‐dihydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 3 ), 2β‐(angeloyloxy)‐8α‐hydroxyeremophila‐7(11),9(10)‐dien‐12,8β‐olide ( 4 ), and 8β‐amino‐10β‐hydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 5 ). In addition, the relative configuration of 1 was corroborated by X‐ray diffraction analysis.     

Antioxidant, anti-glycation and anti-inflammatory activities of phenolic constituents from Cordia sinensis

Nine compounds have been isolated from the ethyl acetate soluble fraction of C. sinensis, namely protocatechuic acid (1), trans-caffeic acid (2), methyl rosmarinate (3), rosmarinic acid (4), kaempferide-3-O-β-D-glucopyranoside (5), kaempferol-3-O-β-D-glucopyranoside (6), quercetin-3-O-β-D-glucopyranoside (7), kaempferide-3-O-α-L-rhamnopyranosyl (1→6)-β-D-glucopyranoside (8) and kaempferol-3-O-α-L-rhamno-pyranosyl (1→6)-β-D-glucopyranoside (9), all reported for the first time from this species. The structures of these compounds were deduced on the basis of spectroscopic studies, including 1D and 2D NMR techniques. Compounds 1-9 were investigated for biological activity and showed significant anti-inflammatory activity in the carrageen induced rat paw edema test. The antioxidant activities of isolated compounds 1-9 were evaluated by the DPPH radical scavenging test, and compounds 1, 2, 4 and 7-9 exhibited marked scavenging activity compared to the standard BHA. These compounds were further studied for their anti-glycation properties and some compounds showed significant anti-glycation inhibitory activity. The purity of compounds 2-5, 8 and 9 was confirmed by HPLC. The implications of these results for the chemotaxonomic studies of the genus Cordia have also been discussed.     

蒺藜果化学成分的分离和鉴定

分离鉴定了2个六糖呋甾皂苷, 其中化合物1为新化合物.     

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.     

Terpenoids from the barks of Magnolia maudiae (Dunn) Figlar

A new germacrenolide (1) and fourteen known terpenoids (2–15) were isolated from the barks of Magnolia maudiae (Dunn) Figlar (Magnoliaceae). The structure of (7αH,11βH)-2α,8α-dihydroxy-4α,5β-epoxy-germacr-1(10)-en-6α,12-olide (1) was elucidated by physical and spectroscopic data analysis, including 1D, 2D NMR and HR-ESI-MS. Lyratol F (9) was isolated from Magnolia for the first time. The structures of known compounds were established by comparing their spectroscopic data with those in literatures.     

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 ).     

Two New Triterpene and a New Nortriterpene Glycosides from Phlomis viscosa

The isolation and structure elucidation of two new oleanane‐type triterpene glycosides, 29‐(β‐D ‐glucopyranosyloxy)‐2α,3β,23‐trihydroxyolean‐12‐en‐28‐oic acid (=(2α,3β,4α,29α)‐29‐(β‐D ‐glucopyranosyloxy)‐2,3,23‐trihydroxyolean‐12‐en‐28‐oic acid; 1 ) and its C(20)‐epimer, 30‐(β‐D ‐glucopyranosyloxy)‐2α,3β,23‐trihydroxyolean‐12‐en‐28‐oic acid (=(2α,3β,4α,29β)‐29‐β‐D ‐glucopyranosyloxy)‐2,3,23‐trihydroxyolean‐12‐en‐28‐oic acid; 2 ), and a novel nortriterpene glycoside, (17S)‐2α,18β,23‐trihydroxy‐3,19‐dioxo‐19(18→17)‐ abeo‐28‐norolean‐12‐en‐25‐oic acid β‐D ‐glucopyranosyl ester (=(1R,2S,4aS,4bR,6aR,7R,9R,10aS,10bS)‐3,4,4a,4b,5,6,6a,7,8,9,10,10a,10b,11‐tetradecahydro‐1‐hydroxy‐7‐(hydroxymethyl)‐3′,4′,4a,4b,7‐pentamethyl‐2′,8‐ dioxospiro[chrysene‐2(1H),1′‐cyclopentane]‐10a‐carboxylic acid β‐D ‐glucopyranosyl ester; 3 ) from Phlomis viscosa (Lamiaceae) are reported. The structures of the compounds were asigned by means of spectroscopic (IR, 1D‐ and 2D‐NMR, and LC‐ESI‐MS) and chemical (acetylation) methods.