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.     

Itosides A – I,New Phenolic Glycosides from Itoa orientalis

Eight new benzoylated gentisyl alcohol (=2‐(hydroxymethyl)benzene‐1,4‐diol) glucosides, itosides A–H ( 1 – 8 ), together with the new pyrocatechol (=benzene‐1,2‐diol) glycoside itoside I ( 9 ) were isolated from the bark and twigs of Itoa orientalis (Flacourtiaceae). In itosides B–D ( 2 – 4 ), the gentisyl alcohol moiety was esterified by 1‐hydroxy‐6‐oxocyclohex‐2‐ene‐1‐carboxylic acid, while itosides E–H ( 5 – 8 ) contained instead an additional 2‐hydroxybenzoic acid moiety. The compounds were accompanied by the known derivatives 4‐hydroxytremulacin ( 10 ), poliothyrsoside ( 11 ), poliothyrsin ( 12 ), homaloside D ( 13 ), tremulacin, and pyrocatechol β‐D ‐glucopyranoside. The structures of the new compounds were elucidated by spectral and chemical methods.     

Furanone Derivatives from Aspergillus sp. XW‐12, an Endophytic Fungus in Huperzia serrata

Two new 5‐methoxyfuran‐3(2H)‐one derivatives, huaspenone A ( 1 ) and B ( 2 ), together with four known ones, i.e., aspertetronin A ( 3 ), aspertetronin B ( 4 ), gregatin E ( 5 ), and penicilliol A ( 6 ), were isolated from the cultures of an endophytic fungus Aspergillus sp. XW‐12, derived from the stems of Huperzia serrata. The structures of the new isolates were established by detailed interpretation of the 1D‐ and 2D‐NMR and HR‐ESI‐MS data.     

Tetrapterosides A and B,two new oleanane‐type saponins from Tetrapleura tetraptera

From the stem bark of Tetrapleura tetraptera, two new oleanane‐type saponins, tetrapteroside A 3‐O‐{6‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐hydroxyocta‐2,7‐dienoyl]‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranosyl‐(1 → 3)‐β‐D ‐glucopyranosyl‐(1 → 4)‐[β‐D ‐glucopyranosyl‐(1 → 2)]‐β‐D ‐glucopyranosyl}‐3,27‐dihydroxyoleanolic acid (1), and tetrapteroside B 3‐O‐{ β‐D ‐glucopyranosyl‐(1 → 2)‐6‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranosyl‐(1 → 3)‐β‐D ‐glucopyranosyl‐(1 → 4)‐[β‐D ‐glucopyranosyl‐(1 → 2)]‐β‐D ‐glucopyranosyl}‐3,27‐dihydroxyoleanolic acid (2), were isolated. Further extractions from the roots led to the isolation of four known oleanane‐type saponins. Their structures were elucidated by the combination of mass spectrometry (MS), one and two‐dimensional NMR experiments. Copyright © 2009 John Wiley & Sons, Ltd.     

Neoengleromycin,a Novel Compound from Engleromyces goetzii

A novel N‐containing compound, neoengleromycin ( 1 ) was isolated from the fruiting bodies of the ascomycete Engleromyces goetzii together with two known cytochalasins: cytochalasin D ( 2 ) and 19,20‐epoxycytochalasin D ( 3 ). Structures were established by spectroscopic (including 2D‐NMR) and chemical means. Neoengleromycin ( 1 ) possesses the rare structure of an N‐substituted hydroxamic acid and represents a new type of natural products.     

Beilschmiedic Acids F and G,Further Endiandric Acid Derivatives from Beilschmiedia anacardioides

Two new endiandric acid derivatives, beilschmiedic acid F ( 1 ) and beilschmiedic acid G ( 2 ), together with three known constituents, beilschmiedic acid A, beilschmiedic acid C, and sitosterol 3‐β‐D ‐glucopyranoside, were isolated from the stem bark of Beilschmiedia anacardioides. Their structures were elucidated mainly by using a combination of 1D‐ and 2D‐NMR techniques. The structure and relative configuration of beilschmiedic acid G ( 2 ) was also confirmed by X‐ray crystallographic analysis.     

Three New Lanostane Triterpenoids,Inonotsutriols A,B, and C,from Inonotus obliquus

Three new lanostane‐type triterpenoids, inonotsutriols A ( 1 ), B ( 2 ), and C ( 3 ) were isolated from the sclerotia of Inonotus obliquus (Pers .: Fr.) (Japanese name: kabanoanatake; Russian name: chaga). Their structures were determined to be (3β,21R,24S)‐21,24‐cyclolanost‐8‐ene‐3,21,25‐triol ( 1 ), (3β,21R,24R)‐21,24‐cyclolanost‐8‐ene‐3,21,25‐triol ( 2 ), and (3β,21R,24S)‐21,24‐cyclolanosta‐7,9(11)‐diene‐3,21,25‐triol ( 3 ) on the basis of NMR spectroscopy including 1D and 2D experiments (¹H,¹H‐COSY, NOESY, HMQC, and HMBC) and EI‐MS.     

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.     

Lanostane Triterpenes from Ceriporia lacerate HS‐ZJUT‐C13A,a Fungal Endophyte of Huperzia serrata

Two new lanostane triterpenes, 3β‐acetoxy‐15α‐hydroxylanosta‐8,24‐dien‐21‐oic acid ( 1 ) and 3β‐acetoxylanosta‐7,9(11),24‐trien‐21‐oic acid ( 2 ), along with the four known analogs, 3 – 6 , were isolated from the culture broth of Ceriporia lacerate HS‐ZJUT‐C13A, a fungal endophyte residing in the stems of the traditional Chinese herb Huperzia serrata. The structures of the new compounds 1 and 2 were established by spectroscopic methods, including UV, IR, HR‐ESI‐MS, and extensive 1D‐ and 2D‐NMR techniques. To the best of our knowledge, this is the first report on triterpene metabolites from the genus Ceriporia.     

Novel,Complex Flavonoids from Mallotus philippensis (Kamala Tree)

One new flavanone, 4′‐hydroxyisorottlerin ( 2 ), and two new chalcone derivatives, kamalachalcones C ( 3 ) and D ( 4 ), were isolated from Mallotus philippensis (kamala tree). The largest compound ( 4 ; M_r 1098 g/mol) was shown to possess a unique, fused‐ring system made of two hydroxy‐chalcone units, giving rise to eight fused benzene/pyran units. From the same plant, the following six known compounds were also isolated: kamalachalcone A ( 5 ) and B ( 6 ), isoallorottlerin ( 7 ), isorottlerin ( 8 ), 5,7‐dihydroxy‐8‐methyl‐6‐prenylflavanone ( 9 ); 6,6‐dimethylpyrano(2″,3″: 7,6)‐5‐hydroxy‐8‐methylflavanone ( 10 ), and rottlerin ( 1 ). The structures of the new compounds were confirmed by in‐depth spectral analyses, including 2D‐NMR techniques, and the full ¹³C‐NMR assignments of the known flavanones 1 and 7 – 10 are published for the first time.     

Three New, 1‐Oxygenated ent‐8,9‐Secokaurane Diterpenes from Croton kongensis

Three new ent‐8,9‐secokaurane diterpenes, kongensins A–C ( 1 – 3 ), were isolated from the aerial parts of Croton kongensis, together with two known compounds, rabdoumbrosanin ( 4 ) and (7α,14β)‐7,14‐dihydroxy‐ent‐kaur‐16‐en‐15‐one ( 5 ). The structures of the new compounds were elucidated by HR‐MS as well as in‐depth 1D‐ and 2D‐NMR analyses. Compounds 1 – 3 showed an unusual oxygenation pattern, with an AcO or OH group at C(1), in combination with a Δ⁸⁽¹⁴⁾ unsaturation ( 1 ) or an 8,14‐epoxide function ( 2, 3 ).     

Hypenol,a New Lignan from Hypenia salzmannii

A new lignan, (?)‐secoisolariciresin‐9‐yl 6‐O‐p‐coumaroyl‐β‐D ‐glucopyranoside ( 1 ), named hypenol, along with eleven known compounds, i.e., hyperin, rosmarinic acid, methyl rosmarinate, a mixture of the triterpenes betulinic acid, ursolic acid, and oleanolic acid, glycosylated β‐sitosterol, a mixture of the flavanones sakuranetin and isosakuranetin, hinokinin, and β‐peltatin A dimethyl ether were isolated from the EtOH extract of the leaves of Hypenia salzmannii (Benth. ) Harley . The structures of the compounds were elucidated based on the analysis of spectral data, including MS, 1D‐ and 2D‐NMR, and comparison with data in the literature.     

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.).     

Epunctanone,a New Benzophenone,and Further Secondary Metabolites from Garcinia epunctata Stapf (Guttiferae)

A new polyprenylated benzophenone, named epunctanone ( 1 ), was isolated from the stem bark of Garcinia epunctata Stapf , together with eight known compounds, 7‐epiisogarcinol ( 2 ), 2,6‐dimethoxy‐p‐benzoquinone ( 3 ), friedelin ( 4 ), lupeol ( 5 ), 16β‐hydroxylupeol ( 6 ), betulin ( 7 ), stigmasterol ( 8 ), and rheediaxanthone A ( 9 ). The structure of epunctanone ( 1 ) was established by detailed analysis of its spectroscopic data, especially 1D‐ and 2D‐NMR, and HR‐MS data. All these compounds were evaluated for their antimicrobial and anti‐protozoan activities. They were also assayed to determine if any of the compounds were nonpeptide agonist ligands for nematodal G‐protein‐coupled receptors, which would be an indication of potential antinematodal activity. Among the isolated compounds, 7‐epiisogarcinol ( 2 ) was the most active against Candida albicans.     

Two New Endiandric Acid Analogs,a New Benzopyran,and a New Benzenoid from the Root of Beilschmiedia erythrophloia

Phytochemical investigation of the root of Beilschmiedia erythrophloia led to the isolation and structural elucidation of two new endiandric acid analogs, endiandric acids I and J ( 1 and 2 , resp.), a new benzopyran, dehydrooligandrol methyl ether ( 3 ), and a new benzenoid, farnesylol ( 4 ), together with six known compounds. Their structures were established on the basis of extensive 1D‐ and 2D‐NMR analyses in combination with HR‐MS experiments.     

Scyphiphorins A and B,Two New Iridoid Glycosides from the Stem Bark of a Chinese Mangrove Scyphiphora hydrophyllacea

Two new iridoid glycosides, named scyphiphorins A ( 1 ) and B ( 2 ), together with four known compounds, geniposidic acid (=(1S,4aS,7aS)‐1‐(β‐D ‐glucopyranosyloxy)‐1,4a,5,7a‐tetrahydro‐7‐(hydroxymethyl)cyclopenta[c]pyran‐4‐carboxylic acid; 3 ), 4‐(4‐hydroxy‐3‐methoxybenzyl)butan‐2‐one, oleanolic acid (=(3β)‐3‐hydroxyolean‐12‐en‐28‐oic acid), and stigmasterol β‐D ‐glucoside (=(3β,22E)‐stigmasta‐5,22‐dien‐3‐yl β‐D ‐glucopyranoside), were isolated for the first time from the stem bark of a Chinese mangrove, Scyphiphora hydrophyllacea Gaertn . f. The structures of compounds 1 and 2 were determined as 10‐O‐benzoylgeniposidic acid and 10‐O‐[(2E,6R)‐8‐hydroxy‐2,6‐dimethyl‐1‐oxooct‐2‐en‐1‐yl]geniposidic acid, respectively, on the basis of spectroscopic data and chemical methods, including 2D NMR techniques.     

Three New Triterpenes from Xylarialean sp. A45, an Endophytic Fungus from Annona squamosa L.

From the fermentation extract of Xylarialean sp. A45, an endophytic fungus of Annona squamosa L., three new triterpenes, namely xylariacins A–C ( 1 – 3 , resp.) were obtained. Their structures were determined by spectroscopic analyses, including 1D‐ and 2D‐NMR experiments and HR‐ESI‐Q‐TOF mass spectrometry. The in vitro cytotoxic activities of compounds 1 – 3 were tested against human tumor cell line HepG2, and these compounds showed modest cytotoxic activity.     

Two New Iridoids from the Stem of Catalpa ovata

Two new iridoids, 6‐O‐[(E)‐feruloyl]jioglutin D ( 1 ) and 6‐O‐(4‐hydroxybenzoyl)jioglutin D ( 2 ), and six known compounds, minecoside ( 3 ), specioside ( 4 ), picroside II ( 5 ), picroside III ( 6 ), 4‐hydroxybenzoic acid ( 7 ), and martynoside ( 8 ), were isolated from the stem of Catalpa ovata. The structures of the new compounds were established on the basis of spectroscopic techniques, including 1D‐ and 2D‐NMR.     

Diketopiperazine Alkaloids from Penicillium spp. HS‐3, an Endophytic Fungus in Huperzia serrata

Cultivation of the fungus Penicillium spp. HS‐3, an endophytic fungus from the stems of Huperzia serrata, led to the isolation of a new diketopiperazine alkaloid, named as tryhistatin ( 1 ), together with three known ones, 2 – 4 , all of which share a similar backbone. The structure of 1 was established by detailed interpretation of the 1D‐ and 2D‐NMR spectra, and HR‐ESI‐MS data. Furthermore, 1D‐ and 2D‐NMR experiments were employed to elucidate the structure of 2 which was deduced previously only on the basis of the LC/MS method. In this article, we confirmed the correctness of the previously reported structure and made a complete assignment of the NMR signals of 2 for the first time.     

Two New, 1‐Oxygenated ent‐Kaurane‐Type Diterpenes from Croton kongensis

One new ent‐8,9‐secokaurane diterpene, kongensin D ( 1 ), and one new ent‐kaurane diterpene, kongensin E ( 2 ), along with one known compound, (7α)‐7,18‐dihydroxy‐ent‐kaur‐16‐en‐15‐one 18‐acetate ( 3 ), were isolated from the aerial parts of Croton kongensis. The structures of the new compounds were elucidated by means of HR‐MS and in‐depth NMR experiments, and by comparison with literature data. Compounds 1 and 2 showed an unusual oxygenation pattern with an OH or AcO group at C(1).