Sterols from the Fungus Catathelasma imperiale

Eight ergostane-type sterols and three their derivatives (one mono-linoleate and two mono-glucosides) were isolated from the ethyl acetate soluble fraction of the fungus Catathelasma imperi.a/e. Two of them are novel compounds, namely 22E,24R-er-gosta-7,22-diene-3β ,5α-diol-6β-linoleate (1) and 22E, 24R-er-gosta-7,22-diene-3β, 5β, 6α-triol (5) with an uncommon c/s-fused A/B ring. Structures of these compounds were demon-strated on the basis of their chemical evidences and spectroscop-ic methods, especially 2D NMR techniques.     

New Steryl Esters of Fatty Acids from the Mangrove Fungus Aspergillus awamori

The polyhydroxylated ergostane‐type sterol 9 , its derivatives 10 – 15 , and the fatty acid esters 1 – 8 were isolated from a fungus strain which was collected from mangrove areas at Wenchang, Hainan Province, P. R. China, exhibited potent cytotoxic activity, and was identified as Aspergillus awamori. The structures of 1 – 15 were elucidated by spectroscopic and chemical methods. Among them, the six steryl esters 1 – 6 of fatty acids were new compounds, i.e., (3β,5α,6α,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐palmitate ( 1 ), (3β,5α,6α,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐stearate ( 2 ), (3β,5α,6α,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐oleate ( 3 ), (3β,5α,6α,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐linoleate ( 4 ), (3β,5α,6β,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐palmitate ( 5 ), and (3β,5α,6β,22E)‐ergosta‐7,22‐diene‐3,5,6‐triol 6‐stearate ( 6 ). The related known fatty acids stearic acid (=octadecanoic acid) and palmitic acid (=octadecanoic acid) were also obtained. A speculative biogenetic relationship of the metabolites is proposed. The known polyhydroxylated sterols and derivatives showed cytotoxic activities, in agreement with earlier reports. The cytotoxic activities against B16 and SMMC‐7721 cell lines of the new steryl esters 1 – 6 by the MTT method were weak.     

Withanolides from Physalis alkekengi var. francheti

Two new withanolides, namely (20S,22R)‐15α‐acetoxy‐5α‐chloro‐6β,14β‐dihydroxy‐1‐oxowitha‐2,24‐dienolide ( 1 ) and (22R)‐5β,6β : 14α,17 : 14β,26‐triepoxy‐2α‐ethoxy‐13,20,22‐trihydroxy‐1,15‐dioxo‐16α,24‐cyclo‐13,14‐secoergosta‐18,27‐dioic acid 18→20,27→22‐dilactone ( 2 ), along with six known compounds, physagulin B ( 3 ), withangulatin A ( 4 ), physalin I ( 5 ), withaminimin ( 6 ), physagulin J ( 7 ), and ergosta‐5,25‐diene‐3β,24ξ‐diol ( 8 ), were isolated from the whole plant of Physalis alkekengi var. francheti. Their structures were elucidated on the basis of spectroscopic analyses.     

Two New Ring A‐Cleaved Lanostane‐Type Triterpenoids and Four Known Steroids Isolated from Endophytic Fungus Glomerella sp. F00244

Two new ring A‐cleaved lanostane‐type triterpenoids, glometenoid A ( 1 ) and glometenoid B ( 2 ), together with four known steroids, (20S,22E,24R)‐ergosta‐7,22‐dien‐3β,5α,6β‐triol ( 3 ), (3β,5α,8α,22E)‐ergosta‐6,22‐diene‐3,5,8‐triol ( 4 ), 5α,8α‐epidioxy‐22E‐ergosta‐6,22‐dien‐3β‐ol ( 5 ), and ergosterol ( 6 ), were isolated from the endophytic fungus Glomerella sp. F00244. Their structures were elucidated by comprehensive spectroscopic analyses of NMR and MS data. Their antimicrobial activities were evaluated against pathogenic bacteria Bacillus subtilis ATCC 9372, Staphylococcus aureus ATCC 25923, Bacillus pumilus CMCC (B) 63202, Micrococcus luteus CMCC28001, and pathogenic fungi Candida albicans AS2.538 and Aspergillus niger ACCC30005, but no inhibition was observed at a concentration of 20 μg/ml. Further cytotoxicity assessment revealed that compound 1 exhibited weak antiproliferative activity against ovarian cancer HeLa cell.     

Cucurbitane‐type triterpene glycosides from the fruits of Momordica charantia

The chemical study of Momordica charantia fruits led to the isolation of three new cucurbitane triterpene glycosides, momordicosides U, V, and W (1–3). The structures of these compounds were determined to be (19R, 23R)‐5β, 19‐epoxy‐19‐methoxycucurbita‐6,24‐diene‐3β, 23‐diol 3‐O‐β‐D‐allopyranoside (1), (23R)‐5β, 19‐epoxycucurbita‐6,24‐diene‐3β, 23‐diol 3‐O‐β‐D‐allopyranoside (2), and (19R)‐5β, 19‐epoxy‐19,25‐dihydroxycucurbita‐6,23(E)‐diene‐3β‐ol 3‐O‐β‐D‐glucopyranoside (3), by chemical and spectroscopic methods. Copyright © 2010 John Wiley & Sons, Ltd.     

Neoclerodane Diterpenes from Amoora stellato‐squamosa

From the twigs of Amoora stellato‐squamosa, five new neoclerodane diterpenes have been isolated and characterized, methyl (13E)‐2‐oxoneocleroda‐3,13‐dien‐15‐oate (=methyl (2E)‐3‐methyl‐5‐[(1S,2R,4aR,8aR)‐1,2,3,4,4a,7,8,8a‐octahydro‐1,2,4a,5‐tetramethyl‐7‐oxo‐naphthalen‐1‐yl]pent‐2‐enoate; 1 ), (13E)‐2‐oxoneocleroda‐3,13‐dien‐15‐ol (=(4aR,7R,8S,8aR)‐1,2,4a,5,6,7,8,8a‐octahydro‐8‐[(E)‐5‐hydroxy‐3‐methylpent‐3‐enyl]‐4,4a,7,8‐tetramethylnaphthalen‐2(1H)‐one; 2 ), (3α,4β,13E)‐neoclerod‐13‐ene‐3,4,15‐triol (=(1R,2R,4aR, 5S,6R,8aR)‐decahydro‐5‐[(E)‐5‐hydroxy‐3‐methylpent‐3‐enyl]‐1,5,6,8a‐tetramethylnaphthalene‐1,2‐diol; 3 ), (3α,4β,13E)‐4‐ethoxyneoclerod‐13‐ene‐3,15‐diol (=(1R,2R,4aR,5S,6R,8aR)‐1‐ethoxydecahydro‐5‐[(E)‐5‐hydroxy‐3‐methylpent‐3‐enyl]‐1,5,6,8a‐tetramethylnaphthalen‐2‐ol; 4 ), and (3α,4β,14RS)‐neoclerod‐13(16)‐ ene‐3,4,14,15‐tetrol (=(1R,2R,4aR,5S,6R,8aR)‐decahydro‐5‐[3‐(1,2‐dihydroxyethyl)but‐3‐enyl]‐1,5,6,8a‐tetramethylnaphthalene‐1,2‐diol; 5 ), together with two known compounds, (13E)‐neocleroda‐3,13‐diene‐15,18‐diol ( 6 ) and (13S)‐2‐oxoneocleroda‐3,14‐dien‐13‐ol ( 7 ).     

Hydrolytic Reaction of Plant Extracts to Generate Molecular Diversity: New Dammarane Glycosides from the Mild Acid Hydrolysate of Root Saponins of Panax notoginseng

Molecular diversity was generated by hydrolyzing the crude root saponins of Panax notoginseng (Burk .) F. H. Chen under mild acidic condition (AcOH/EtOH 1 : 1). From the acid hydrolysate, five new dammarane glycosides, named notoginsenoside T₁ (=(3β,6α,12β,20E,23RS)‐24,25‐epoxy‐6‐[(β‐D ‐glucopyranosyl)oxy]‐dammar‐20(22)‐ene‐3,12,23‐triol; 1 ), notoginsenoside T₂ (=(3β,6α,12β,20E,23RS)‐24,25‐epoxy‐6‐[(β‐D ‐glucopyranosyl)oxy]‐23‐methoxydammar‐20(22)‐ene‐3,12‐diol; 2 ), notoginsenoside T₃ (=(3β,6α,12β,20S)‐6‐[(β‐D ‐glucopyranosyl)oxy]‐20‐ethoxydammar‐24‐ene‐3,12‐diol; 3 ), notoginsenoside T₄ (=(3β,6α,12β,20S,22E,24RS)‐6‐[(β‐D ‐glucopyranosyl)oxy]dammar‐22‐ene‐3,12,20,24,25‐pentol; 4 ), and notoginsenoside T₅ (=(3β,6α,12β, 24E)‐6‐[(β‐D ‐xylopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl)oxy]dammara‐20(21),24‐diene‐3,12‐diol; 5 ), were isolated, together with 15 known dammarane glycosides, and their structures were elucidated on the basis of spectroscopic evidence. Among the known compounds, ginsenosides Rg₃ and Rh₁ were isolated as major constituents, in addition to ginsenosides Rg₅, Rh₄, and a mixture of (20R)‐ and (20S)‐25‐hydroxyginsenoside Rh₁, all of which were obtained from P. notoginseng for the first time.     

A new natural nucleotide and other antibacterial metabolites from an endophytic Nocardia sp.

Nine compounds were isolated from Nocardia sp. YIM 64630, and their structures were elucidated as 5′-O-acetyl-2′-deoxyuridine (1), 22E,24R-5α,6α-epoxyergosta-8(14),22-diene-3β,7α-diol (2), 22E,24R-5α,6α-epoxyergosta-8,22-diene-3β,7α-diol (3), 22E,24R-ergosta-7,22-diene-3β,5α,6β-triol (4), 5α,8α-epidioxyergosta-6,22-dien-3β-ol (5), 4′,5,6-trihydroxy-7-methoxyisoflavone (6), 2,4,4′-trihydroxy-deoxybenzoin (7), methyl [4-hydroxyphenyl]acetate (8) and daidzein by extensive spectroscopic analyses. Compound 1 was isolated from natural resources for the first time. The antimicrobial and antioxidant activities of compounds 1–8 were investigated.     

A Rare New Cleistanthane Diterpene from the Pericarp of Trewia nudiflora

A minor, unprecedented diterpene, 3β,17‐dihydroxycleistantha‐12,15‐dien‐2‐one ( 1 ), was isolated from the CHCl₃‐soluble part of the EtOH extract of the pericarp of Trewia nudiflora. The structure of 1 was elucidated by means of 1D‐ and 2D‐NMR spectroscopic analyses as well as by HR‐MS. Also isolated were two known triterpenes, glutin‐5‐en‐3‐ol and olean‐18‐en‐3‐one (germanicone), as well as three known sterols, (22E,24R)‐5α,8α‐epidioxyergosta‐6,22‐dien‐3β‐ol, (22E,24R)‐5α,8α‐epidioxyergosta‐6,9(11),22‐trien‐3β‐ol, and (22E,24R)‐6‐methoxyergosta‐7,22‐dien‐3,5‐diol.     

Dolabellane Diterpenoids from the Higher Plant Aglaia odorata

Two new dolabellane diterpenoids, (1R,3R,7E,11S,12R)‐dolabella‐4(16),7‐diene‐3,18‐diol ( 1 ) and (1R,3E,7R,11S,12R)‐dolabella‐3,8(17)‐diene‐7,18‐diol ( 2 ), and the known (1R,3E,7E,11S,12R)‐dolabella‐3,7‐dien‐18‐ol ( 3 ) were isolated from Aglaia odorata, along with twelve other known compounds. Their structures were elucidated on the basis of spectroscopic data. This is the first time that dolabellane‐type diterpenoids were detected in higher plants.     

New oxidized sterols from Aspergillus awamori and the endo‐boat conformation adopted by the cyclohexene oxide system

Two new oxidized sterols 1 and 2 were obtained from the active fraction of a mangrove fungus Aspergillus awamori isolated from the soils around the mangrove plant Acrostichum speciosum. Their structures were elucidated using spectroscopic methods as 22E‐7α‐methoxy‐5α,6α‐epoxyergosta‐8(14),22‐dien‐3β‐ol (1) and 22E‐3β‐hydroxy‐5α,6α,8α,14α‐diepoxyergosta‐22‐en‐7‐one (2). The NMR data and complete assignments for both DMSO‐d₆ and CDCl₃ were given. Their cytotoxic activity against A549 cell line was evaluated. Furthermore, the detailed conformation analysis for ring B (cyclohexene oxide system) of sterol 1 was given on the basis of NOEs. The endo‐boat conformation was considered as the preferred conformation for ring B rather than half‐chair conformation. Copyright © 2009 John Wiley & Sons, Ltd.     

Two New Tetracyclic Triterpenoids and Other Constituents from Aster Ageratoides var. Oophyllus

Two new tetracyclic triterpenoids shiona‐19(E),21‐dien‐3β‐ol ( 1 ), and shiona‐22(29)‐en‐3β,21‐diol ( 2 ), together with four known compounds shiona‐21‐en‐3β‐ol ( 3 ), friedelinol ( 4 ), β‐sitosterol ( 5 ), and (24R)‐stigmast‐7,22(E)‐dien‐3a‐ol ( 6 ) were isolated from Aster ageratoides var. oophyllus. The structures of two new compounds were established on the basis of IR, MS, ¹H, ¹³C and 2D NMR spectroscopic methods.     

Muurolane‐type sesquiterpenes from marine sponge Dysidea cinerea

Seven new muurolane‐type sesquiterpenes, (4R,5R)‐muurol‐1(6),10(14)‐diene‐4,5‐diol (1), (4R,5R)‐muurol‐1(6)‐ene‐4,5‐diol (2), (4R,5R,10R)‐10‐methoxymuurol‐1(6)‐ene‐4,5‐diol (3), (4S)‐4‐hydroxy‐1,10‐seco‐muurol‐5‐ene‐1,10‐dione (4), (4R)‐4‐hydroxy‐1,10‐seco‐muurol‐5‐ene‐1,10‐dione (5), (6S,10S)‐6,10‐dihydroxy‐7,8‐seco‐2,8‐cyclo‐muurol‐4(5),7(11)‐diene‐12‐oic acid (6), and (6R,10S)‐6,10‐dihydroxy‐7,8‐seco‐2,8‐cyclo‐muurol‐4(5),7(11)‐diene‐12‐oic acid (7) were isolated from the marine sponge Dysidea cinerea. Their structures were determined by the combination of spectroscopic and chemical methods, including 1D‐NMR, 2D‐NMR, and CD spectra as well as by comparing the NMR data with those reported in the literature. Copyright © 2013 John Wiley & Sons, Ltd.     

New Sterol Derivatives from the Marine Sponge Xestospongia sp.

Chemical examination of a marine sponge Xestospongia sp. resulted in the isolation of 20 sterol derivatives ( 1 – 20 ), including eight new sterols namely aragusterols J – L ( 1 – 3 ), (5α,7α,12β,22E)‐7,12,18‐trihydroxystigmast‐22‐en‐3‐one ( 4 ), (5α,7α,12β,24R)‐ and (5α,7α,12β,24S)‐7,12,20‐trihydroxystigmastan‐3‐one ( 5 / 6 ), and (5α,7α,12β,22E,24R)‐ and (5α,7α,12β,22E,24S)‐7,12,20‐trihydroxyergost‐22‐en‐3‐one ( 7 / 8 ). The structures of new compounds were determined through extensive spectroscopic analyses and chemical conversion. The sterol diversity was mainly characterized by the presence of a cyclopropane unit at side chain, while compound 4 with 18‐hydroxymethyl group was found in stigmasterol family for the first time. Cytotoxic test revealed the inhibitory effects of compounds 1 , 4 , and 17 against human leukemia cell line K562 with IC₅₀ values of 18.3, 24.1, and 34.3 μm , respectively.     

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.     

Baimantuoluolines D – F,Three New Withanolides from the Flower of Datura metel L.

Three new withanolide compounds, named baimantuoluolines D–F, along with three known withanolides and a lignan were isolated from the flower of Datura metel L., the parts effective against psoriasis. The structures of the new compounds were elucidated as (5α,6β,12β,20R,22R,24R,25S)‐21,24‐epoxy‐5,6,12‐trihydroxy‐27‐methoxy‐1‐oxowith‐2‐enolide ( 1 ), (5α,6β,12β,20R,22R,24R,25S)‐21,24‐epoxy‐5,6,12,27‐tetrahydroxy‐1‐oxowith‐2‐enolide ( 2 ), and (5α,6β,12β,22R)‐5,6,12,21‐tetrahydroxy‐1‐oxowith‐24‐enolide( 3 ) on the basis of physicochemical evidence.     

Cucurbitane Triterpenoids from the Fruit Pulp of Momordica charantia and Their Cytotoxic Activity

Two new cucurbitane‐type triterpenes, 25‐methoxycucurbita‐5,23(E)‐diene‐3β,19‐diol ( 1 ) and 7β‐ethoxy‐3β‐hydroxy‐25‐methoxycucurbita‐5,23(E)‐dien‐19‐al ( 2 ), together with three known cucurbitane‐type triterpenes, 3β,7β,25‐trihydroxycucurbita‐5,23(E)‐dien‐19‐al ( 3 ), (23E)‐3β‐hydroxy‐7β,25‐dimethoxycucurbita‐5,23‐dien‐19‐al ( 4 ), and 3β‐hydroxy‐25‐methoxycucurbita‐6,23(E)‐dien‐19,5β‐olide ( 5 ), were isolated from the fruit pulp of Momordica charantia. The structures of two new compounds were elucidated on the basis of 1D and 2D NMR, MS, IR, optical rotation. Among these isolates, compounds 1 , 2 , and 5 showed slight cytotoxic activity against the SK‐Hep 1 cell line with IC₅₀ values of 33.1, 24.3, and 38.7 μM, respectively.     

Cytotoxic Activity of Capnellene‐8β, 10α‐Diol Derivatives from a Taiwanese Soft Coral Capnella sp.

The sesquiterpene capnellene‐8β, 10α‐diol ( 1 ) was isolated from non‐polar extract of the soft coral Capnella sp. Ten acylation products of capnellene‐8β, 10α‐diol were prepared: 10α‐hydroxy‐8β‐O‐benzoylcapnellene ( 2 ), 10α‐hydroxy‐8β‐O‐p‐toluoylcapnellene ( 3 ), 10α‐hydroxy‐8β‐O‐4‐chlorobenzoyl‐capnellene ( 4 ), 10α‐hydroxy‐8β‐O‐2‐furoylcapnellene ( 5 ), 10α‐hydroxy‐8β‐O‐2‐thiophenoylcapnellene ( 6 ), 10α‐hydroxy‐8β‐O‐4‐fluorobenzoylcapnellene ( 7 ), 10α‐hydroxy‐8β‐O‐4‐propylbenzoylcapnellene ( 8 ), 10α‐hydroxy‐8β‐O‐cinnamoylcapnellene ( 9 ), 10α‐hydroxy‐8β‐O‐4‐nitrobenzoylcapnellene ( 10 ), and 10α‐hydroxy‐8β‐O‐4‐anisoylcapnellene ( 11 ). The structures of capnellene‐8β, 10α‐diol as well as its derivatives were established through standard spectroscopic analysis. The in vitro cytotoxic activities of the eleven compounds were evaluated against Hela, KB, Daoy, and WiDr human tumor cell lines.     

Ergostane Steroids from Dysoxylum lukii

Phytochemical investigation of the 70% EtOH extract from the stem bark of Dysoxylum lukii led to the isolation of three new ergostane steroids, (3β)‐3,20‐dihydroxyergosta‐5,24(28)‐dien‐7‐one ( 1 ), (3β,4β,7α)‐ergosta‐5,24(28)‐diene‐3,4,7‐triol ( 2 ), and (3β,7α)‐3,20‐dihydroxyergosta‐5,24(28)‐dien‐7‐yl acetate ( 3 ), together with the known compound (3β,4β)‐ergosta‐5,24(28)‐diene‐3,4,20‐triol ( 4 ). Their structures were elucidated on the basis of extensive 1D‐ and 2D‐NMR (COSY, HMQC, HMBC, and NOESY) analyses.     

Sesquiterpenoids and Lactone Derivatives from Ligularia dentata

Seven new compounds were isolated from the roots of Ligularia dentata, including five bisabolane‐type sesquiterpenoids (bisabolane=1‐(1,5‐dimethylhexyl)‐4‐methylcyclohexane), namely (8β,10α)‐8‐(angeloyloxy)‐5,10‐epoxybisabola‐1,3,5,7(14)‐tetraene‐2,4,11‐triol ( 1 ), (8β,10α)‐8‐(angeloyloxy)‐5,10‐epoxythiazolo[5,4‐a]bisabola‐1,3,5,7(14)‐tetraene‐4,11‐diol ( 2 ), (1α,2α,3β,5α,6β)‐1,5,8‐tris(angeloyloxy)‐10,11‐epoxy‐2,3‐dihydroxybisabol‐7(14)‐en‐4‐one ( 3 ), (1α,2α,3β,5α,6β)‐2,5,8‐tris(angeloyloxy)‐10,11‐epoxy‐1,3‐dihydroxybisabol‐7(14)‐en‐4‐one ( 4 ), and (1α,2β,3β,5α,6β)‐1,8‐bis(angeloyloxy)‐2,3‐epoxy‐5,10‐dihydroxy‐11‐methoxybisabol‐7(14)‐en‐4‐one ( 5 ) (angeloyloxy=[(2Z)‐2‐methyl‐1‐oxobut‐2‐enyl]oxy), and two lactone derivatives, (2α,3β,5α)‐2‐(acetyloxy)‐9‐methoxy‐5‐(methoxycarbonyl)‐2,3‐dimethylheptano‐5‐lactone ( 6 ), and (2β,4β)‐2‐ethyl‐5‐hydroxy‐5‐(methoxycarbonyl)‐4,5‐dimethylpentano‐4‐lactone ( 7 ) (α/β denote relative configurations), together with (2E,4R,5S)‐2‐ethylidene‐5‐(methoxycarbonyl)‐4‐methylhexano‐5‐lactone ( 8 ), a known synthetic compound. Compound 2 is the first sesquiterpenoid derivative containing the uncommon benzothiazole moiety. The structures of 1 – 8 were established by spectroscopic methods, especially 2D‐NMR and MS analyses.