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.     

Foetidissimosides C–F,Novel Glycosides from the Roots of Cucurbita foetidissima

Two novel echinocystic acid (=(3β,16α)‐3,16‐dihydroxyolean‐12‐en‐28‐oic acid) glycosides, foetidissimosides C ( 1 ), and D ( 2 ), along with new cucurbitane glycosides, i.e., foetidissimosides E/F ( 3 / 4 ) as an 1 : 1 mixture of the (24R)/(24S) epimers, were obtained from the roots of Cucurbita foetidissima. Their structures were elucidated by means of a combination of homo‐ and heteronuclear 2D‐NMR techniques (COSY, TOCSY, NOESY, ROESY, HSQC, and HMBC), and by FAB‐MS. The new compounds were characterized as (3β,16α)‐28‐{[O‐β‐D ‐glucopyranosyl‐(1→3)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐6‐deoxy‐α‐L ‐mannopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl]oxy}‐16‐hydroxy‐28‐oxoolean ‐12‐en‐3‐yl β‐D ‐glucopyranosiduronic acid ( 1 ), (3β,16α)‐16‐hydroxy‐28‐oxo‐28‐{{O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐[β‐D ‐xylopyranosyl‐(1→4)]‐O‐6‐deoxy‐α‐L ‐mannopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl}oxy}olean‐12‐en‐3‐yl β‐D ‐glucopyranosiduronic acid ( 2 ), and (3β,9β,10α,11α,24R)‐ and (3β,9β,10α,11α,24S)‐25‐(β‐D ‐glucopyranosyloxy)‐9‐methyl‐19‐norlanost‐5‐en‐3‐yl 2‐O‐β‐D ‐glucopyranosyl‐β‐D ‐glucopyranoside ( 3 and 4 , resp.).     

Three New 24‐Noroleanane Triterpenoids from Quercus aliena var. acuteserrata

Three new 24‐noroleanane triterpenoids, i.e., 2α,19α‐dihydroxy‐3‐oxo‐24‐norolean‐12‐en‐28‐oic acid ( 1 ) and 19α‐hydroxy‐3‐oxo‐24‐norolean‐12‐en‐28‐oic acid ( 2 ), and 2α,3β,19α‐trihydroxy‐24‐norolean‐12‐en‐28‐oic acid ( 3 ) were isolated from Quercus aliena var. acuteserrata, together with three known compounds, bartogenic acid ( 4 ), ilexgenin A ( 5 ), and aophitolic acid ( 6 ). Their structures were established by spectroscopic methods, especially 2D‐NMR and MS analyses.     

Chemical Constituents from the Roots of Schnabelia tetradonta

The new rearranged‐abietane diterpene 1 , the four new triterpenoids 2 – 5 , and the new aminoethylphenyl oligoglycoside 6 , besides 19 known compounds, were isolated from the roots of Schnabelia tetradonta, a Chinese endemic herb. The structures of the new compounds were elucidated on the basis of spectroscopic evidence as 12,17‐epoxy‐11,14,16‐trihydroxy‐17(15→16)‐abeo‐abieta‐8,11,13,15‐tetraen‐7‐one ( 1 ), 21β‐(β‐D ‐glucopyranosyloxy)‐2α,3α‐dihydroxyolean‐12‐en‐28‐oic acid ( 2 ), 2β,3β,16β‐trihydroxy‐15‐oxo‐28‐norolean‐12‐en‐23‐oic acid ( 3 ), 3β‐[(4‐O‐acetyl‐β‐D ‐glucopyranuronosyl)oxy]‐2β,16β‐dihydroxy‐28‐norolean‐15‐oxo‐12‐en‐23‐oic acid ( 4 ), 3β‐[(4‐O‐acetyl‐6‐O‐methyl‐β‐D ‐glucopyranuronosyl)oxy]‐2β,16β‐dihydroxy‐15‐oxo‐28‐norolean‐12‐en‐23‐oic acid ( 5 ), and 4‐[2‐(acetylamino)ethyl]phenyl O‐6‐O‐[(Z)‐p‐methoxycinnamoyl]‐β‐D ‐glucopyranosyl‐(1→2)]‐O‐[β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐acetyl‐α‐L ‐rhamnopyranoside ( 6 ), respectively.     

Chemical Constituents from Annona Glabra

A new kaurane diterpenoid, annoglabasin G (16α‐hydro‐19‐acetoxy‐ent‐kauran‐17‐al) ( 1 ), along with 27 compounds including 18 kaurane diterpenoids, 16β‐hydro‐ent‐kauran‐17‐oic acid ( 2 ), 16α‐hydro‐ent‐kauran‐17‐oic acid ( 3 ), 19‐nor‐ent‐kauran‐4α‐ol‐17‐oic acid ( 4 ), 16α‐hydro‐19‐ol‐ent‐kauran‐17‐oic acid ( 5 ), ent‐kaur‐16‐en‐19‐oic acid ( 6 ), 16α‐hydroxy‐ent‐kauran‐19‐oic acid ( 7 ), 16α,17‐dihydroxy‐ent‐kauran‐19‐oic acid ( 8 ), 16β,17‐dihydroxy‐ent‐kauran‐19‐oic acid ( 9 ), 16α‐hydro‐ent‐kauran‐17,19‐dioic acid ( 10 ), 16β‐hydroxy‐17‐acetoxy‐ent‐kauran‐19‐oic acid ( 11 ), 16β‐hydro‐17‐hydroxy‐ent‐kauran‐19‐al ( 12 ), 16α‐hydro‐17‐hydroxy‐ent‐kauran‐19‐al ( 13 ), 16β,17‐dihydroxy‐ent‐kauran‐19‐al ( 14 ), 16α‐hydro‐19‐al‐ent‐kauran‐17‐oic acid ( 15 ), 16α‐hydro‐17‐acetoxy‐ent‐kauran‐19‐al ( 16 ), 16α‐hydro‐19‐acetoxy‐ent‐kauran‐17‐oic acid ( 17 ), ent‐kaur‐15‐en‐19‐oic acid ( 18 ) and ent‐kaur‐15‐en‐17‐ol‐19‐oic acid ( 19 ); four acetogenins, annomontacin ( 20 ), annonacin ( 21 ), isoannonacinone ( 22 ) and squamocin ( 23 ); four steroids, β‐sitosterol ( 24 ), stigmasterol ( 25 ), β‐sitosteryl‐D‐glucoside ( 26 ) and stigmasteryl‐D‐glucoside ( 27 ) and one oxoaporphine, liriodenine ( 28 ), were isolated from the fresh fruits of Annona glabra. These compounds were characterized and identified by physical and spectral evidence.     

The Constituents of Lindera Glauca

Twenty‐eight compounds including seven alkaloids, (+)‐3‐chloro‐N‐formylnornantenine ( 1 ), (+)‐N‐formylnornantenine ( 2 ), (+)‐boldine ( 3 ), (+)‐norboldine ( 4 ), (‐)‐norboldine ( 5 ), lycicamine ( 6 ), and tetrahydroberberine ( 7 ); four flavonoids, kaempferol ( 8 ), kaempferol‐3‐O‐arabinoside ( 9 ), quercetin ( 10 ), and quercetin‐3‐O‐rhamnoside ( 11 ); one butanolide, akolactone A ( 12 ); one p‐quinone, 2,6‐dimethoxy‐p‐quinone ( 13 ); one cyclohex‐2‐en‐1‐one, blumenol A ( 14 ); six benzenoids, methylparaben ( 15 ), p‐hydroxybenzoic acid ( 16 ), vanillic acid ( 17 ), syringic acid ( 18 ), 3,4,5‐trimethoxybenzoic acid ( 19 ), and 3‐(3,4‐dihydroxyphenyl) propionic acid ( 20 ); one diterpene, phytol ( 21 ); one triterpene, squalene ( 22 ); six steroids, (3‐sitosterol ( 23 ), β‐sitostenone ( 24 ), stigmasta‐4,22‐dien‐3‐one ( 25 ), 6β‐hydroxy‐β‐sitostenone ( 26 ), 6β‐hydroxystigmasterone ( 27 ), and β‐sitosteryl‐D‐glucoside ( 28 ) were isolated from the aerial part of Lindera glauca. These compounds were characterized and identified by physical and spectral method. All compounds were isolated for the first time from this plant. Among them, (+)‐3‐chloro‐N‐formylnornantenine ( 1 ) is a new one.     

Metabolites with Cytotoxic Activity from the Formosan Soft Coral Cladiella Australis

The metabolites, (24S)‐3β‐acetoxyergost‐5‐en‐21‐oic acid ( 2 ), 5′‐O‐acetylthymidine ( 3 ), 3′‐O‐acetylthymidine ( 4 ), and p‐vinylbenzyl alcohol ( 5 ), along with a known steroid ( 1 ) were isolated from the EtOAc extract of the Formosan soft coral Caldiella australis. The structures of new metabolites were determined on the basis of spectroscopic (including 1D and 2D NMR) analyses and by comparison of their NMR spectral data with those of related compounds. Except for 3 , all compounds exhibited cytotoxic activity of various degrees of potency against a limited panel of human liver and breast cancer cell lines.     

Structure elucidation and complete NMR spectral assignments of two new oleanane‐type pentacyclic triterpenoid saponins from the husks of Xanthoceras sorbifolia Bunge

Two new saponins were isolated from husks of Xanthoceras sorbifolia Bunge and their structures were elucidated as 3‐O‐[β‐D‐galactopyranosyl(1→2)]‐α‐L‐arabinofuranosyl(1→3)‐β‐D‐methyl glucuronic acid‐21‐O‐(3,4‐diangeloyl)‐α‐L‐rhamnose‐3β, 16α, 21β, 22α, 28β‐pentahydroxyl‐22‐acetoxy‐olean‐12‐ene(1) and 3‐O‐[β‐D‐galactopyranosyl(1→2)]‐α‐L‐arabinofuranosyl(1→3)‐β‐D‐methyl glucuronic acid‐21,22‐O‐diangeloyl‐3β,15α,16α,21β,22α,28β‐hexahydroxyl‐olean‐12‐ene(2) on the basis of 1D and 2D NMR (including ¹H, ¹³C‐NMR, ¹H? ¹H COSY, HSQC, HMBC and DEPT), ESI‐MS spectrometry and chemical methods. Copyright © 2009 John Wiley & Sons, Ltd.     

Triterpenoid Saponins from the Spikes of Prunella vulgaris

Three new oleanane‐skeleton triterpenoid saponins, 3β,4β,16α‐17‐carboxy‐16,24‐dihydroxy‐28‐norolean‐12‐en‐3‐yl 4‐O‐β‐D ‐xylopyranosyl‐β‐D ‐glucopyranosiduronic acid ( 1 ), (3β,4β,16α)‐17‐carboxy‐16,24‐dihydroxy‐28‐norolean‐12‐en‐3‐yl β‐D ‐glucopyranosiduronic acid methyl ester ( 2 ), and (3β,4β)‐24‐hydroxy‐16‐oxo‐28‐norolean‐12‐en‐3‐yl 4‐O‐β‐D ‐xylopyranosyl‐β‐D ‐glucopyranosiduronic acid ( 3 ), together with eight known constituents, i.e., the oleanane‐type triterpenoids 4 – 6 , and the ursane‐type triterpenoids 7 – 11 , were isolated from the spikes of Prunella vulgaris. The new structures were established by means of detailed spectroscopic analysis (IR, HR‐ESI‐MS, 1D‐ and 2D‐NMR experiments). Compounds 1 – 3 were tested for their inhibition activity against the growth of tumor cell lines; only compound 3 displayed marginal inhibition activity.     

Sterols from the Stems of Momordica charantia

A new sterol, 5α,6α‐epoxy‐3β‐hydroxy‐(22E,24R)‐ergosta‐8,22‐dien‐7‐one ( 1 ), together with eight known sterols, 5α,6α‐epoxy‐(22E,24R)‐ergosta‐8,22‐diene‐3β,7α‐diol ( 2 ), 5α,6α‐epoxy‐(22E,24R)‐ergosta‐8,22‐diene‐3β,7β‐diol ( 3 ), 5α,6α‐epoxy‐(22E,24R)‐ergosta‐8(14),22‐diene‐3β,7α‐diol ( 4 ), 3β‐hydroxy‐(22E,24R)‐ergosta‐5,8,22‐trien‐7‐one ( 5 ), ergosterol peroxide ( 6 ), clerosterol ( 7 ), decortinol ( 8 ), and decortinone ( 9 ), were isolated from the stems of Momordica charantia. Their structures were elucidated by mean of extensive spectroscopic methods, including ¹H, ¹³C, 2D‐NMR and HR‐EI‐MS, as well as comparison with the literature data. Compounds 1 , 4 , 5 , 8 , and 91 were not cytotoxic against the SK‐Hep 1 cell line.     

Chemical Constituents of Ailanthus triphysa

Two new compounds,8(14),15-isopimaradiene-2α，３α，19-triol(1),and 6α，７β－dihydroxy-17(20)-cis-5α－pregna-16-one(2),together with four known copounds,a oxygenated rare phyllocladane,phyllocladan-16α，19-diol(3),kaempferol-3-0-β－Ｄ-galactopyranosied,kaempferol-3-0-α－Ｌ－rhamnopyranoside and scopoletin, were isolated from the leaves of Ailanthus tripysa.Structures of 1-3 were elucidated on the basis of spectroscopic data as compared with related compounds.     

A Diterpenoid with a New Skeleton and Cytotoxic Terpenoids Isolated from Amentotaxus formosana

The new diterpenoid 6α‐hydroxy‐ent‐kaur‐16‐en‐15‐one ( 1 ) and a diterpenoid with a new skeleton, i.e., amentotaxin BB ( 5 ), as well as three new lanostanoids, i.e., (3β,23R)‐3‐methoxy‐24‐methylenelanost‐8‐en‐23‐ol ( 6 ), (23S)‐23‐methoxy‐24‐methylenelanost‐8‐en‐3‐one ( 7 ), and (3β,24ξ)‐3‐methoxy‐24‐methyl‐9,19‐cyclolanostan‐25‐ol ( 8 ), were isolated from the bark and leaves of Amentotaxus formosana. Their structures, including the relative configurations, were elucidated from spectroscopic data. Compound 1 and a known compound, ent‐kaur‐16‐en‐15‐one ( 2 ), showed potent cytotoxic effects against a number of cancer cells in vitro.     

Theoretical study of structural features of endo,exo double bonds and side chain in 14α‐demethylation of lanosterol

The 14α‐demethylation of biosynthetic reactions is carried out exclusively by lanosta‐8,24‐dien‐3β‐ol (lanosterol). Theoretical calculations were done to determine the importance of this structure with the Hartree–Fock scheme. It was modeled on structures similar to lanosterol with variations on the endo between C8? C9 (lanosta‐7,24‐dien‐3β‐ol and lanosta‐6,24‐dien‐3β‐ol) as compared with the exo between C24? C25 (Lanosta‐8‐en‐3β‐ol) and the size of the side chain (27‐norlanosta‐8‐en‐3β‐ol, 26,27‐dinorlanosta‐8‐en‐3β‐ol, 25,26,27‐trinorlanosta‐8‐en‐3β‐ol, 24,25,26,27‐tetranorlanosta‐8‐en‐3β‐ol, 23,24,25,26,27‐pentanorlanosta‐8‐en‐3β‐ol, 22,23,24,25,26,27‐hexanorlanosta‐8‐en‐3β‐ol). Energetic, electronic, and orbital evidence was found. The theoretical data were analyzed and were found to be important for the 14α‐demethylation, the presence of HOMO on the region C8? C9 and C14? C14¹, a negative charge on the outgoing methyl C14¹. This atomic charge varies with the size of the side chain, and with the modification of the endo and exo double bonds. The conformation of the structure of the steroid is also related to its reactivity. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

New Sesquiterpenes from Ligulariopsis Shichuana

A thorough investigation of Ligulariopsis shichuana afforded five new sesquiterpenes, including 1β,10β‐epoxy‐3α‐angeloyloxy‐9β‐acetoxy‐8α,11β‐dihydroxybakkenolide ( 1 ), 1β,7‐dihydroxy‐3β‐acetoxy‐noreremophil‐6(7),9(10)‐dien‐8‐one ( 2 ), 8α‐hydroxy‐3‐oxoeremophil‐1(2),7(11),9(10)‐trien‐8β(12)‐olide ( 3 ), 1β,10β‐dihydroxy‐3β‐acetoxyeremophil‐7(11),8(9)‐dien‐8(12)‐olide ( 4 ) and 1β,10β‐epoxy‐8,12‐dihydroxy‐3β‐acetoxy‐9β‐angeloyloxyeremophil‐7(11)‐en‐8,12‐disemiketal ( 5 ). Their structures were established by spectroscopic methods and 2D NMR techniques. In addition, bakkenolide ( 1 ) and eremophilenolides ( 5 ) showed antibacterial and cytotoxic activities.     

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.     

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.     

Terpenoids from the Flower of Cacalia Tangutica

A thorough investigation of Cacalia tangutica (Franch.) Hand‐Mazz afforded two new epimeric eremophilane sesquiterpenoids, 7β‐ H‐3α‐angeloyloxy‐9‐ene‐11,12‐epoxy‐8‐oxoeremophilane ( 1 ) and 7α‐H‐3α‐angeloyloxy‐9‐ene‐11,12‐epoxy‐8‐oxoeremophilane ( 2 ), as well as four known sesquiterpenes, petasol ( 3 ), oplopanone ( 4 ), 4,5‐epoxy‐β‐caryophyllene ( 5 ), 4(15)‐eudesmene‐1β,6α‐diol ( 6 ), and three known monoterpenes, 1β,2α‐dihydroxy‐p‐menth‐5‐ene ( 7 ), 5α‐hydroxy‐2‐oxo‐p‐menth‐6(1)‐ene ( 8 ), 5β‐hydroxy‐2‐oxo‐p‐menth‐6(1)‐ene ( 9 ), and two known triterpenes, maniladiol 3‐O‐palmitate ( 10 ), taraxasteryl palmitate ( 11 ). The new compounds were characterized by means of spectroscopic methods including 1D, 2D NMR and HRESIMS, and the known ones were established on the basis of comparing their NMR data with those of the corresponding compounds in the literature. In addition, cytotoxicity against selected cancer cells (HL‐60, HO‐8910 and A‐549) of compounds 1 ‐ 4 , 6 , 7 , 10 were measured in vitro.     

Triterpenoids from the Roots of Camellia oleifera C.Abel and Their Cytotoxic Activities

Three new triterpenoids, 21β,22α‐diangeloyloxy‐3β,15α,16α,28‐tetrahydroxyolean‐12‐en‐23‐al ( 1 ), 21β‐angeloyloxy‐3β,15α,16α,28‐tetrahydroxy‐22α‐(2‐methylbutanoyloxy)olean‐12‐en‐23‐al ( 2 ), and 21β‐angeloyloxy‐3β,16α,28‐trihydroxy‐22α‐(2‐methylbutanoyloxy)olean‐12‐en‐23‐al ( 3 ), along with six known triterpenoids, were isolated from the roots of Camellia oleifera C.Abel . The structures of compounds 1 – 3 were elucidated on the basis of spectroscopic analyses. Moreover, all compounds isolated were evaluated for their cytotoxic activities by MTT (=3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐2H‐tetrazolium bromide) assay.     

Two New Diterpenoids and other Constituents from Isodon Nervosus

Two new ent‐kaurane diterpenoids, 15β‐hydroxy‐6,7‐seco‐6,11β:6,20‐diepoxy‐1α,7‐olide‐ent‐kaur‐16‐ene ( 1 ), 11α,15α‐dihydroxy‐6β‐methoxy‐6,7‐seco‐6,20‐epoxy‐1α,7‐olide‐ent‐kaur‐16‐ene ( 2 ), together with four known diterpenoids, nodosin ( 3 ), isodocarpin ( 4 ), odonicin ( 5 ) and maoyecrystal F ( 6 ) were isolated from the aerial parts of Isodon nervosus. The structures of the new compounds were elucidated on the basis of their spectral evidence, especially on 2D NMR.     

One Alkenylphenol and Steroids from the Aquatic Plant Monochoria Vaginalis

Two new compounds have been isolated from the whole plant of Monochoria vaginalis and characterized as: (10Z)‐1‐(2,6‐dihydroxyphenyl)octadec‐10‐en‐1‐one ( 1 ) (20R, 24R)‐campest‐5‐ene‐3β, 4β‐diol ( 2 ) together with nine known ones. The structures of these compounds were elucidated on the basis of spectral data and chemical evidence.