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 .     

Nortriterpenoids from Schisandra wilsoniana

Three new highly oxygenated nortriterpenoids, wilsonianadilactones A–C ( 1 – 3 ), together with twelve known ones, i.e., 4 – 15 , were isolated from the leaves and stems of Schisandra wilsoniana. Their structures were established by means of extensive analysis of spectroscopic data, and compound 1 was further confirmed by X‐ray crystallographic diffraction. Compounds 1 – 3 showed weak anti‐HIV‐1 activity with EC₅₀ values of 23.5, 55.5, and 66.4 μg/ml, respectively.     

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.     

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.     

NMR‐Solution Structures and Affinities for the Human Somatostatin G‐Protein‐Coupled Receptors hsst1–5 of CF3 Derivatives of Sandostatin® (Octreotide)

The previously reported (Helv. Chim. Acta 2008 , 91, 2035) derivatives of octreotide ( 1 ) with a (CF₃)‐Trp substitution, i.e., 3 , and with open‐chain structures, i.e., 2, 4 , and 5 , have been tested for their affinities to hsst_1–5 receptors and subjected to a detailed NMR analysis. Their affinities vary from 15 nM to 5 μM , as compared to 0.6 nM to 0.8 μM for octreotide itself (Table 1). This decreased bioactivity may have had to be expected for the open‐chain compounds 4 and 5 ; possible reasons for this decrease in the case of CF₃ derivative of octreotide, 3 , are discussed. NMR Analysis (Tables 2 and 3) provides evidence for increased dynamics of all new derivatives 2 – 5 . The dynamics of the octreotide molecule 1 was analyzed by (natural‐abundance) longitudinal ¹³C‐T₁‐relaxation time measurements (Table 4), from which the conclusion is drawn that the backbone of the macrocycle is rather rigid on the time scale of this method.     

Chromenone Glucosides Acylated with Monoterpene Acids from the Leaves of Eucalyptus camaldulensis var. obtusa

Three new chromenone glucosides acylated with monoterpene acids, eucamaldusides A ( 1 ), B ( 2 ), and C ( 3 ), were isolated from the leaves of Eucalyptus camaldulensis var. obtusa, together with the five known compounds ursolic acid lactone, obtusilin, β‐sitosterol glucoside, 4‐hydroxybenzoic acid, and cypellocarpin C. The structures of the new compounds were established by exhaustive 1D‐ and 2D‐NMR spectroscopic studies. Their configuration was determined by measuring the [α]_D of the known methyl esters of the monoterpene acids obtained by methanolysis of 1 – 3 .     

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.     

Huangqiyenins G – J,Four New 9,10‐Secocycloartane (=9,19‐Cyclo‐9,10‐secolanostane) Triterpenoidal Saponins from Astragalus membranaceus Bunge Leaves

Four new 9,10‐secocycloartane (=9,19‐cyclo‐9,10‐secolanostane) triterpenoidal saponins, named huangqiyenins G–J ( 1 – 4 , resp.), were isolated from Astragalus membranaceus Bunge leaves. The acid hydrolysis of 1 – 4 with 1M aqueous HCl yielded D ‐glucose, which was identified by GC analysis after treatment with L ‐cysteine methyl ester hydrochloride. The structures of 1 – 4 were established by detailed spectroscopic analysis as (3β,6α,10α,16β,24E)‐3,6‐bis(acetyloxy)‐10,16‐dihydroxy‐12‐oxo‐9,19‐cyclo‐9,10‐secolanosta‐9(11),24‐dien‐26‐yl β‐D ‐glucopyranoside ( 1 ), (3β,6a,10α,24E)‐3,6‐bis(acetyloxy)‐10‐hydroxy‐12,16‐dioxo‐9,19‐cyclo‐9,10‐secolanosta‐9(11),24‐dien‐26‐yl β‐D ‐glucopyranoside ( 2 ), (3β,6α,9α,10α,16β,24E)‐3,6‐bis(acetyloxy)‐9,10,16‐trihydroxy‐9,19‐cyclo‐9,10‐secolanosta‐11,24‐dien‐26‐yl β‐D ‐glucopyranoside ( 3 ), and (3β,6α,10α,24E)‐3,6‐bis(acetyloxy)‐10‐hydroxy‐16‐oxo‐9,19‐cyclo‐9,10‐secolanosta‐9(11),24‐dien‐26‐yl β‐D ‐glucopyranoside ( 4 ).     

Four New Cucurbitacins from the Fruit of Momordica charantia

Four new 5β,19‐epoxycucurbitacins, kuguacins T–W ( 1 – 4 , resp.), along with nine known cucurbitane derivatives, 5 – 13 , were obtained from the fresh fruit of Momordica chrantia. Structures of the new metabolites were elucidated as 5β,19‐epoxy‐25‐hydroxycucurbitane‐3,7,23‐trione ( 1 ), 5β,19‐epoxy‐3,7‐dioxo‐23,24,25,26,27‐pentanorcucurbitan‐22‐oic acid ( 2 ), 5β,19‐epoxy‐3β‐hydroxycucurbit‐24‐ene‐7,23‐dione ( 3 ), and 5β,19‐epoxy‐25‐hydroxycucurbit‐23‐ene‐3,7‐dione ( 4 ), by extensive spectroscopic investigations, which were confirmed by a single‐crystal X‐ray diffraction analyses in the case of compound 4 .     

Vinmajorines C – E,Monoterpenoid Indole Alkaloids from Vinca major

Three new monoterpenoid indole alkaloids, vinmajorines C–E ( 1 – 3 ), along with 18 known analogues ( 4 – 21 ), were isolated from the whole plants of Vinca major. The new structures were elucidated as (5α,15β,16R,17α,19β,20α,21β)‐10,17‐dimethoxy‐21‐methyl‐18‐oxa‐5,16‐cycloyohimban‐19‐ol ( 1 ), (5α,15β,16R,17α,20α,21β)‐10‐methoxy‐21‐methyl‐18‐oxa‐5,16‐cycloyohimban‐17‐ol ( 2 ), and (5α,15β,16R,17α,20α,21β)‐10‐methoxy‐21‐methyl‐18‐oxa‐5,16‐cycloyohimban‐17‐yl acetate ( 3 ), respectively, by extensive NMR and MS analysis and comparison with known compounds. Compounds 1 – 3 were evaluated for their cytotoxic activities against five human cancer cell lines, compounds 1 and 3 showing moderate cytotoxic activities.     

Flavonoid Constituents from Spiraea brahuica

Sparins A–C ( 1 – 3 , resp.), three new flavonoids, were isolated from the CHCl₃ subfraction of the EtOH extract of the whole plant of Spiraea brahuica, along with 3′,7‐di‐O‐methylquercetin ( 4 ) and luteolin 7‐β‐D ‐glucopyranoside ( 5 ), reported for the first time from this species. The structures of the new compounds were elucidated by spectroscopic techniques including MS and 2D‐NMR spectroscopy.     

Five New Aromatic Glycosides from Carthamus tinctorius

Five new aromatic glycosides, 1 – 5 , named as carthamosides B₄–B₈, together with three known compounds, 4′‐(hydroxyphenacyl)‐β‐D ‐glucopyranoside ( 6 ), benzyl‐O‐α‐L ‐rhamnopyranosyl‐(1→6)‐β‐D ‐glucopyranoside ( 7 ), and 4‐(methoxybenzyl)‐O‐β‐D ‐glucopyranoside ( 8 ), have been isolated from the air‐dried flower of Carthamus tinctorius. Their structures were identified on the basis of chemical and spectroscopic methods.     

Four New Pregnane Steroids from Aglaia abbreviata and Their Cytotoxic Activities

Four new pregnane steroids, aglaiasterols A–D ( 1 – 4 ), have been isolated from the EtOH extract of stems of Aglaia abbreviata. They were identified as (3α,5α,17Z)‐3‐hydroxypregn‐17‐en‐16‐one ( 1 ), (3β,5α,17E)‐3‐hydroxypregn‐17‐en‐16‐one ( 2 ), (3β,5α,17Z)‐3‐hydroxypregn‐17‐en‐16‐one ( 3 ), and (3α,5α,20S*)‐3‐hydroxy‐16‐oxopregnan‐20‐yl acetate ( 4 ) on the basis of spectroscopic methods, including 1D‐ and 2D‐NMR techniques. Compounds 1 – 4 were evaluated for their cytotoxic activities against K562 (human leukemia), MCF‐7 (human breast cancer), and KB (human oral epithelium cancer) cells, and drug‐resistant cells of K562/A02, MCF‐7/ADM, and KB/VCR. These isolates showed weak to moderate inhibitory effects on the growth of the tested cell lines.     

Three New Dimeric Orcinol Glucosides from Curculigo orchioides

Three new phenolic glucosides named orcinosides A, B, and C ( 1, 2 , and 3 , resp.) were isolated in low yields (4.0×10⁻⁶, 11.5×10⁻⁶, 4.5×10⁻⁶%, resp.) from the rhizomes of Curculigo orchioides. Their structures were elucidated by comprehensive spectroscopic analyses including FAB‐MS, HR‐ESI‐MS, IR, and 1D‐ and 2D‐NMR (HSQC, HMBC) data. Compounds 1 – 3 contained two orcinol‐glucoside moieties linked through a CH₂ group.     

Triterpene Saponins from Entada phaseoloides

Four oleanane‐type triterpene saponins, phaseoloideside A–D ( 1 – 4 ), were isolated from the seed kernels of Entada phaseoloides, along with rheediinoside B. The structures of the four new compounds were established by 2D‐NMR spectroscopic methods, HR‐ESI‐MS analysis, and chemical degradation. Phaseoloideside D ( 4 ) showed cytotoxic activity against the Eca‐109 cell line with an IC₅₀ value of 28.0 μM .     

Eupatozansins A – C,Sesquiterpene Lactones from Eupatorium chinense var. tozanense

Phytochemical investigation of Eupatorium chinense var. tozanense has resulted in the isolation of three new germacranolides, designated as eupatozansins A–C ( 1 – 3 ), along with five known compounds, (5S,6R,7R,8R)‐8‐angeloyloxy‐2‐oxoguaia‐1(10),3,11(13)‐trien‐12,6‐olide ( 4 ), costunolide ( 5 ), leptocarpin ( 6 ), 2α‐hydroxyeupatolide 8‐O‐angelate ( 7 ), and quercetin ( 8 ). The structures of the new compounds were identified by 1D and 2D NMR experiments, as well as high‐resolution mass spectrometry. The in vitro cytotoxic activities of compounds 1 – 8 were evaluated.     

Three New 24‐Nortriterpenoids from the Roots of Ilex asprella

Asprellols A–C ( 1 – 3 , resp.), three new 24‐nortriterpenoids, were isolated from the CHCl₃‐soluble fraction of 95% EtOH extract of the roots of Ilex asprella, together with a known nortriterpenoid. The structures of the new compounds were elucidated as 2,6β,20β‐trihydroxy‐3‐oxo‐11α,12α‐epoxy‐24‐norursa‐1,4‐dien‐28,13β‐olide ( 1 ), 2,6β‐dihydroxy‐3‐oxo‐11α,12α‐epoxy‐24‐norursa‐1,4,20(30)‐trien‐28,13β‐olide ( 2 ), and 2,6β‐dihydroxy‐3‐oxo‐11α,12α‐epoxy‐24‐noroleana‐1,4‐dien‐28,13β‐olide ( 3 ) on the basis of spectroscopic analyses.     

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 Polyyne (=Polyacetylene) Glucosides from the Edible Roots of Codonopsis cordifolioidea

Three new linear C₁₄ polyyne (=polyacetylene) glucosides, cordifolioidynes A–C ( 1 – 3 ), together with two known polyynes, lobetyol ( 4 ) and lobetyolin ( 5 ), and five known phenylpropanoids, i.e., sinapinaldehyde ( 6 ), coniferaldehyde ( 7 ), coniferoside ( 8 ), sachaliside ( 9 ), and isoconiferin ( 10 ), were isolated from the roots of Codonopsis cordifolioidea. The structures of 1 – 3 were established from spectral evidences and by characterization of their hydrolysis products. Acid hydrolysis of 1 afforded the aglycone 1a , while hydrolysis of 2 and 3 gave the cyclization products 2a and 3a , respectively. Compounds 4 – 10 were isolated from this plant for the first time. The antibacterial activity of compounds 1 – 5 were assessed against eight microbial strains by the agar dilution method, none of them exhibited antibacterial effects at concentrations up to 100 μg/ml.     

Further Withaphysalin Derivatives from Acnistus arborescens

Two new epimeric chlorinated withaphysalins, rel‐(4β,5β,6α,18S,22R)‐ and rel‐(4β,5β,6α,18R,22R)‐6‐chloro‐18,20‐epoxy‐18‐ethoxy‐4,5‐dihydroxy‐1‐oxowitha‐2,24‐diene‐26,22‐lactone ( 1 and 2 resp.), together with the new rel‐(4β,5β,6α,18R,22R)‐6‐chloro‐18,20‐epoxy‐4,5‐dihydroxy‐18‐methoxy‐1‐oxowitha‐2,24‐diene‐26,22‐lactone ( 3 ) and rel‐(3β,4β,5β,6β,18R,22R)‐5,6:18,20‐diepoxy‐3,18‐diethoxy‐4‐hydroxy‐1‐oxowith‐24‐ene‐26,22‐lactone ( 4 ) were isolated from the leaves of Acnistus arborescens and named withaphysalins T–W, respectively. The final structures and the complete ¹H‐ and ¹³C‐NMR assignments of the three chlorowithaphysalins 1 – 3 were performed by means of HR‐ESI‐MS and 1D‐ and 2D‐NMR experiments, including COSY, HSQC, and HMBC, beside comparison with spectral data of analogous compounds from the literature. The structure of 4 was also confirmed by means of a single‐crystal X‐ray diffraction analysis.