Benzofuranoid Neolignans from Piper kadsura

In a continuing research for neolignans from Piper kadsura (Choisy) Ohwi, six benzofuranoid neolignans were isolated from the aerial part of the plant. Their structure determination were based on the spectroscopic analysis (UV, IR, MS, NMR and CD) and derivative synthesis. Three of the isolated compounds were identified as new structures: 7R, 8R, 1′S-△8′-3, 4-methylenedioxy-5′-methoxy-l′, 4′-dihydro-4′-oxo-7, 0, 2′, 8. l′-neolignan ( Ⅰ ), 7 R, 8 R, 1 ′ R- △8′ - 3,4- methylenedioxy- 1 ′- methoxy - 1′,6′- dihydro- 6′- oxo- 7.0.4′,8. 3′-neolignan (Ⅳ) and 7R, 8R, 1′S-△8′-3, 4-methylenedioxy-l′-methoxy-1′,6′-dihydro-6′-oxo-7.0.4′,8.3′-neolignan (Ⅴ). Known compounds among them are 7R, 8S,1′S-△8′-3, 4-methylenedioxy-5′-methoxy-1′, 4′-dihydro-4′-oxo-7. 0. 2′, 8. 1′-neolignan(Ⅱ), 7S, 8S, 1′R-△8′-3, 4, 5′-trimethoxy-1′, 4′-dihydro-4′-oxo-7.0. 2′, 8. 1′-neolignan (Ⅲ) and 75, 85, 1′S-△8′-3, 4, l′-trimethoxy-l′, 6′-dihydro-6′-oxo-7. 0. 4′, 8. 3′-neolignans (Ⅵ). All of them were isolated from the plant for the first time.     

臭参化学成分的研究

从臭参(Codonopsis cordifolioidea)的根中首次分离鉴定了7个已知化合物,通过波谱学数据结合理化性质分别鉴定为(+)-pinoresinol(1),丁香脂素[(+)-syringgaresinol](2),(+)-lariciresinol(3),3-methoxy-3′,4,9,9′tertrahydroxy-4′,7-epoxy-5′,8-lignan(4),erigeside B(5),pulmatin(6)和(E)-2-hexenyl β-sophoriside(7).     

晶帽石斛的化学成分研究

该研究利用硅胶、凝胶、MCI、中压制备色谱(MPLC)和高效液相半制备色谱(semi-HPLC)等方法,对晶帽石斛(Dendrobium crystallinum)进行了化学成分研究。结果表明:提纯、分离共得到10个化合物,经波谱数据分析及与文献数据对照,分别鉴定为石斛酚(1),3,4'-二羟基-5-甲氧基联苄(2),3,4',5-三羟基-3-甲氧基联苄(3),二氢藜芦醇(4),安告佛醇(5),3',5,7-三羟基-4'-甲氧基黄烷酮(6),4',5,7-三羟基-6-甲氧基黄烷酮(7),丁香树脂醇(8),β-谷甾醇(9),β-胡萝卜苷(10)。其中,除化合物2和化合物10以外,其余8个化合物均在该种植物中首次发现。     

Neolignans from mezilaurus itauba

The wood bark of Mezilaurus itauba afforded in addition to seven known neolignans, three new compounds rel-(7R,8R,1′S,3′S)-Δ^5′,8′-5′-methoxy-3,4-methylenedioxy-1′,2′,3′,4′-tetrahydro-2′,4′-dioxo-7.3′,8.1′-neolignan, rel-(7S,8S,1′S, 2′S, 3′R, 4′S)-Δ^8′-2′,4′-dihydroxy-3,4-methylenedioxy-1′,2′,3′,4′,5′,6′-hexahydro-5′-oxo-7.3′,8.1′-neolignan and rel-(7S,8S)-Δ^8′-6′-hydroxy 5′-methoxy-3,4-methylenedioxy-7·O·2′,8.3′-neolignan. The latter compound has been detected previously in Aniba terminalis. The structures were elucidated by spectroscopic methods and comparison with related compounds.     

Eusiderins and other neolignans from an Aniba species

A previous report disclosed the presence of benzodioxan and bicyclo[3.2.1]octanoid neolignans in the benzene extract of the trunk wood of an Amazonian Aniba (Lauraceae) species. The chloroform extract of the same material contains additionally two new benzodioxan neolignans [rel-(7S,8R)-Δ^8′-7-hydroxy-3,4,5,5′-tetramethoxy-7.0.3′,8.0.4′-neolignan; rel-(7R,8R)-Δ^7′-3,4,5,5′-tetramethoxy-9′-oxo-7.0.3′,8.0.4′-neolignan], two new bicyclo[3.2.1]-octanoid neolignans [(7R,8S,1′S,2′S,3′S,4′R)-Δ^8′-2′,4′-dihydroxy-3,3′-dimethoxy-4,5-methylenedioxy-1′,2′,3′,4′,5′,6′-hexahydro-5′-oxo-7.3′,8.1′-neolignan; (7R,8S,1′R,2′S,3′S)-Δ^8′-2′-hydroxy-3,3′,5′-trimethoxy-4,5-methylenedioxy-1′,2′,3′,4′-tetrahydro-4′-oxo-7.3′,8.1′-neolignan] and a hydrobenzofuranoid neolignan [(7S,8R,1′S,5′S)-Δ^8′-3,3′,5′-tri-methoxy-4,5-methylenedioxy-1′,4′,5′,6′-tetrahydro-4′-oxo-7.0.2′,8.1-neolignan].     

Flavonoids from Lysidice rhodostegia Hance

A novel flavonoid named mopanolchin (1), together with seven known flavonoids, was isolated by various chromatographic techniques and spectroscopic methods from the EtOAc extract of the roots of Lysidice rhodostegia Hance. The structure of the new compound was elucidated as l““““-(4-hydroxy-3, 5-dimethoxy)phenyl-2““““-hydroxymethyl-dioxino [4‘,5‘,1““““,2““““]mopanol (1) on the basis of spectral analysis.The known compounds were identified as (-)-epicatechin-3-O-gallate (2), epicatechin (3), naringenin (4),edodictyol (5), luteolin (6), 7, 3‘, 4‘-trihydroxyflavone (7) and (-)-robinetinidol (8).     

Phenolic compounds from Selaginella moellendorfii

Chemical investigation of the leaves and roots of Selaginella moellendorfii Hieron has resulted in the isolation and characterization of two new flavone glucosides, 7‐O‐(β‐glucopyranosyl(1→2)‐[β‐glucopyranosyl(1→6)]‐β‐glucopyranosyl)flavone‐3′,4′,5,7‐tetraol ( 1 ) and 7‐O‐(β‐glucopyranosyl(1→2)‐[β‐glucopyranosyl(1→6)]‐β‐glucopyranosyl)flavone‐4′,5,7‐triol ( 2 ), two new biflavonoids, 2,3‐dihydroflavone‐5,7,4′‐triol‐(3′→8″)‐flavone‐5″,6″,7″,4′′′‐tetraol ( 3 ) and 6‐methylflavone‐5,7,4′‐triol‐(3′→O→4′′′)‐6″‐methylflavone‐5″,7″‐diol ( 4 ), two new lignans, (7′E)‐3,5,3′,5′‐tetramethoxy‐8 : 4′‐oxyneolign‐7′‐ene‐4,9,9′‐triol ( 5 ) and 3,3′‐dimethoxylign‐8′‐ene‐4,4′,9‐triol ( 6 ), together with two known monolignans, four known lignans, and four known biflavonoids. Their structures were established by spectroscopic means and by comparison with literature values.     

艾纳香化学成分的研究

从艾纳香(Blumea balsamifera DC.)中分离得到12个化合物,通过理化性质和波谱数据分析分别鉴定为;商路素(1),花椒油素(2),2,4-二羟基-6-甲氧基苯乙酮(3),5,7-二羟基色原酮(4),金丝桃苷(5),异槲皮苷(6),3′,4′,5,7-四羟基-3-甲氧基黄酮(7),槲皮素(8),槲皮素-3′-甲氧基-3-O-β-D-半乳吡喃糖苷(9),4′,5,7-三羟基-3,3′-二甲氧基黄酮(10),3,5,7-三羟基-3′,4′-二甲氧基黄酮(11),木犀草素(12).其中,化合物3-7和9- 11为首次从该属植物中分离得到.     

檵木化学成分研究

采用硅胶柱、ODS和凝胶柱色谱进行分离纯化,通过理化方法和波谱分析进行结构鉴定。从檵木(Loro-petalum chinense(R.Br.)oliver)茎叶中分离并鉴定了六个化合物:植物醇(1)、glycerol 1-(14-methlpentadecano-ate)(2)、methyl-(7R,8R)-4-hydroxy-8′,9′-dinor-4′,7-epoxy-8,3′-neolignan-7′-ate(3)、trans-p-coumaric acid ethylester(4)、落叶松树脂酸(laricinolic acid)(5)、tiliroside(6)。除化合物1外,其余化合物均为首次从檵木中分离得到,化合物2、3首次从该属中分离得到。     

鬼针草中一个新的查耳酮甙

从鬼针草BidenspilosaL .地上部分的丙酮提取物中 ,分离鉴定了 1 8个化合物 ,其中包括一个新的查耳酮甙类化合物 (α,3,2′,4′ tetrahydroxy 2′ O β D glucopyranosylchalcone,2 )。其它化合物分别鉴定为butein (1 ) ,okanin 4 methylether 3′ O β glucoside (3) ,sulfuretin (4) ,6 ,7,3′,4′ tetrahydroxyaurone (5) ,海生菊苷 (maritimein ,6) ,(Z ) 6 O (6″ acetyl β D glucopyr anosyl) 6 ,7,3′,4′ tetrahydroxy aurone (7) ,(Z ) 6 O (4″,6″ diacetyl β D glucopyranosyl) 6 ,7,3′,4′ tetrahydroxy aurone (8) ,(Z ) 6 O (3″,4″,6″ triacetyl β D glucopyranosyl) 6 ,7,3′,4′ tetrahydroxy aurone (9) ,木犀草素 (luteolin ,1 0 ) ,槲皮素 (quercetin,1 1 ) ,异槲皮苷 (iso quercitrin,1 2 ) ,芦丁 (rutin,1 3) ,黄芪苷 (astragalin,1 4 ) ,quercetin 3,4′ dimethylether 7 O rutinoside (1 5) ,反式丁烯二酸 (1 6) ,2 β D glucopyranosyloxy 1 hydroxy trideca 3 ,5,7,9,1 1 pentayne (1 7)和 3 β D glucopyranosyloxy 1 hydroxy 6 (E ) tetradecene 8,1 0 ,1 2 triyne (1 8)。     

Neolignans from stem bark of ocotea veraguensis

The stem bark of Ocotea veraguensis has yielded nine neolignans of which five appear to be novel. The new neolignans, which were identified on the basis of spectral characteristics, are^* (7S,8R,1′S,2′S,3′R,4′S)-Δ^8′-2′,4′-dihydroxy-3,3′5′-trimethoxy-4,5-methylenedioxy-1′,2′,3′,4′-tetrahydro-7.3′,8.1′-neolignan, (7S,8R,1′S,3′S,4′S)-Δ^8′-4,4'-dihydroxy-3,3′,5′-trimethoxy-1′,2′,3′,4′-tetrahydro-2′-oxo-7.3′,8.1′-neolignan, (7S,8S,1′R)-Δ^8′-3′,5′-dimethoxy-3,4-methylenedioxy-1′,4′-dihydro-4′-oxo-7.0.2′,8.1′-neolignan, (7S,8S,1′R )-Δ^8′-1′-methoxy-3,4-methylenedioxy-1′,6′-dihydro-6′-oxo-7.0.4′,8.3′-neolignan and (7S,8S)-Δ^8′-2′,6′-dimethoxy-3,4-methylenedioxy-7.0.3′,8.4′,1′.0.7′-neolignan.     

Two new dihydrobenzofuran-type neolignans from Breynia fruticosa

(7S,8R,7′S)-9,7′,9′-Trihydroxy-3,4-methylenedioxy-3′-methoxy [7-O-4′,8-5′] neolignan (1) and (7S,8R,7′S)-9,9′-dihydroxy-3,4-methylenedioxy-3′,7′-dimethoxy [7-O-4′,8-5′] neolignan (2), two new natural dihydrobenzofuran-type neolignans, along with 9,9′-dihydroxy-3,4-methylenedioxy-3′-methoxy [7-O-4′,8-5′] neolignan (3) and (-)-machicendiol (4), were isolated from the whole plants of Breynia fruticosa. The structures of 1 and 2, including the absolute configurations, were determined by spectroscopic methods and circular dichroism (CD) techniques. The absolute configuration of 4 was confirmed by calculations of the OR spectrum, together with OR and ECD spectra of its p-bromobenzoate ester (4a).     

Two polymethoxyflavones from Ageratum houstonianum

Besides agecorynin C, eupalestin and lucidin dimethyl ether, two new highly oxygenated flavones were isolated from Ageratum houstonianum. Their structures were established by spectroscopic and degradative evidence as 5, 6, 7, 8, 2′, 3′, 4′, 5′-octamethoxyflavone and 5, 6, 7, 2′, 3′, 4′, 5′-heptamethoxyflavone.     

Lignan glycosides from the Rhizomes of Smilax trinervula and their Biological activities

Phytochemical investigation of the rhizomes of Smilax trinervula led to isolation and structure elucidation of eight lignan glycosides, including five new lignans, namely, (7S, 8R, 8′R)-4, 4′, 9-trihydroxy-3, 3′, 5, 5′-tetramethoxy-7, 9′-epoxylignan-7′-one 4′-O-β-d-glucopyranoside (1), (7S, 8R, 8′R)-4, 4′, 9-trihydroxy-3, 3′, 5, 5′-tetramethoxy-7, 9′-epoxylignan-7′-one 4-O-β-d- glucopyranoside (2) (7S, 8R)-4, 9, 9′-trihydroxy-3, 3′, 5-trimethoxy-4′, 7-epoxy-8, 5′-neolignan 9′-O-β-d-glucopyranoside (3), (7R, 8R)-4, 9, 9′-trihydroxy-3, 5-dimethoxy-7.O.4′, 8.O.3′- neolignan 9′-O-β-d-glucopyranoside (4), and (7S, 8R)-4, 9, 9′-trihydroxy-3, 3′, 5-trimethoxy-8, 4′-oxy-neolignan 4-O-β-d-glucopyranoside (5), along with three known compounds (6-8). Their structures were established mainly on the basis of 1D and 2D NMR spectral data, ESI–MS and comparison with the literature. Compounds 1-8 were tested in vitro for their cytotoxic activity against four human tumor cell lines (SH-SY5Y, SGC-7901, HCT-116, Lovo). Compounds 3 and 5 exhibited cytotoxic activity against Lovo cells, with IC₅₀ value of 10.4 μM and 8.5 μM, respectively.     

Nucleosides VI: A Novel and Convenient Synthesis of Purine S-Cyclonucleosides Via Mitsunobu Reaction

Abstract

Two representative S-cyclonucleosides, 8,5′-anhydro-2′, 3′-O-isopropylidene-8-mercaptoadenosine (3) and 8,2′-anhydro-3′,5′-O-(tetraisopropyldisiloxane-1,3-diyl)-8-mercaptoguanosine (8), were prepared in good yields by dropwise addition of one equivalent each of triphenylphosphine and DEAD in DMF into a mixture of 2′,3′-O-isopropylidene-8-mercaptoadenosine (2) or 3′,5′-O-(tetra-iso-propyldisiloxane-1,3-diyl)-8-mercaptoguanosine (7), respectively, in DMF. Treatment of compound 2 with two equivalents each of triphenylphosphine and DEAD in DMF afforded N-[8,5′-anhydro-2′,3′-O-isopropylidene-8-mercaptopurin-6-yl]triphenylphospha-λ5-azene (4) in 87% yield.     

肋果茶中的萜类化学成分研究

从肋果茶(Sladenia celastrifolia)95％乙醇提取物的乙酸乙酯部位中分离得到15个萜类化合物,经波谱学方法分别鉴定为sladeniafolin A(1),grasshopper ketone (2),(3S,5R,6S,7E,9R) -7-megastigmene-3,6,9-triol (3),hedytriol (4),(3S,5R,6R,7E,9R) -3,5,6,9-tetrahydroxy-7-megastigmene(5),1′S*,4′R*-8-(4′-hydroxy-2′,6′,6′-trimethylcyclohex-2-enyl)-6-methyloct-3E,5E,7E-trien -2-one (6),2α,3α,19α,23-tetrahydroxyurs-12-en-28-oic acid (7),2α,3β,19α,23-tetrahydroxyurs-12-en-28-oic acid(8),pomolic acid(9),3-O-acetyl pomolic acid(10),ursaldehyde (11),camarolide (12),3β-hydroxyurs-11-en-13β(28) -olide (13),3β-hydroxy -11α,12α-epoxy-urs-13β,28-olide (14)和28-0-β-D-glucopyranosyl euscaphic acid (15).以上化合物均首次从该植物中分离得到,其中1为新的C9裂环烯醚萜.     

Non-alkaloid Constituents of Buxus sinica (Buxaceae)

From the aerial parts of Buxus sinica, ten non- alkaloid compounds were isolated and identified as cleomiscosin A ( 1 ), 3, 5-dihydroxyl-4', 6, 7-trimethyl flavone-3′- O-β- D-glucopyranoside ( 2 ), 3, 5, 3', 4′tetrahydroxyl-3, 6, 7-trimethyl flavone (3 ) , cleomiscosin A-4′- O-β- D-gluco-pyranoside (4 ), 3, 5-dimethoxybenzoicacid-4- O-β- D-glucopyranoside (5 ), 4′, 5-dihydroxyl-3, 6, 7-trimethyl flavone (6), lupine (7), ( + )-pinoresinol- O-β- D-glucopyranoside (8 ), β-sitosterol (9), and daucosterol (10). Their structures were identified by spectral evidence.     

The Chemical Constituents from Podocarpus brevifolius

Ten compounds were isolated from the barks and leaves of Podocarpus brevifolius (Podocarpaceae) for the first time. They are identified as isokaurene (1), △9- isoclextropimaric acid (2), isoginkgetin (3), sciadopitysin (4), amentoflavone-4′,4″′, 7, 7″-tetramethylether (5), sequoyitol (6), β-sitosterol (7), daucosterol (8), β-sitosterone (9), and 3β, 6β-dihydroxy-stigmast-4-ene (10) by means of spectral analysis, comparison of physio-chemical data and throgh chemical method.     

An unusual porosin type neolignan from Licaria chrysophylla

The trunk wood of Licaria chrysophylla contains rel-(7S, 8R, 1′S, 5′S)-Δ^8′-3,3′,5′-trimethoxy-4,5-methylenedioxy-1′,4′,5′,6′- tetrahydro-4′-oxo-7.1′,8.0.2′-neolignan (chrysophyllin A), which differs from all other known benzofuranoid neolignans by showing 7.1′ (rather than 8.1′) and 8.0.2′ (rather than 7.0.2′) linkages between the propenylphenol and allylphenol derived moieties.     

Neolignans from an Aniba species

The trunk wood of an Amazonian Aniba (Lauraceae) species contains, besides dillapiol and the benzodioxane-type neolignan eusiderin, four bicyclo(3.2.1)octanoid neolignans. These comprise representatives of the canellin-type: the known methoxycanellin-A and the novel compounds characterized as (1R, 3S, 4S, 5S, 6S, 7R)-1-allyl-4-hydroxy-3, 5-dimethoxy-7-methyl-6-(3′-methoxy-4′, 5′-methylenedioxyphenyl)-8-oxo-bicyclo(3.2.1)octane; (1R, 3S, 4S, 5S, 6S, 7R)-1-allyl-4-hydroxy-3, 5-dimethoxy-7-methyl-6-(3′, 4′, 5′-trimethoxyphenyl)-8-oxobicyclo(3.2.1)octane and (1R, 4R, 5R, 6S, 7R, 8S)-1-allyl-4, 8-dihydroxy-5-methoxy-7-methyl-6-(3′-methoxy-4′,5′-methylenedioxyphenyl)-3-oxobicyclo(3.2.1)octane.