Three new taxane diterpenoids from the seeds of the Chinese yew, Taxus chinensis var mairei

Three new taxoids were isolated from the seeds of the Chinese yew, Taxus chinesis var mairei, their structures were established as 9alpha, 13alpha-diacetoxy-5alpha-cinnamoyloxy-11(15-->1)-abeo-taxa-4(20),11-diene-10beta, 15-diol, 2alpha,9alpha,10beta-triacetoxy-taxa-4(20),11-diene-5alpha,13alpha-diol and 2alpha,7beta,10beta-triacetoxy-5alpha-cinnamyloxy-9alpha-hydroxy-taxa-4(20),11-diene-13-one on the basis of 1D, 2D NMR, and MS spectral analyses.     

Three new taxoids from the seeds of Japanese yew, Taxus cuspidata

Five taxane diterpenoids were isolated from the seeds of the Japanese yew, Taxus cuspidata Sieb. et Zucc. The structures were established as 2 alpha,7 beta,13 alpha-triacetoxy-5 alpha-(3'-dimethylamino-3'-phenyl)-propionyloxy-2(3-->20)-aboe+ ++-taxa-9,10-dione (1) and 2 alpha,7 beta,9 alpha,10 beta-tetraacetoxy-5 alpha-[(2R,3S),N,N-dimethyl-3-phenylisoseryloxy]-taxa-4(20),11- dien-13-one (2), 2 alpha, 9 alpha, 10 beta-triacetoxy-5 alpha-cinnamoxy-taxa-4(20),11-diene-13 alpha-ol (3), taxezopidine J (4), and taxuspine D (5) on the basis of 1D, 2D NMR, and MS spectral analysis. Compounds 1, 2, and 3 are new compounds.     

Glyyunnansapogenins G and H: Two New Pentacyclic Triterpenoids of the 18alphaH-Oleana-9(11),12-diene Type from Glycyrrhiza yunnanensis Roots

Two new pentacyclic triterpenoid sapogenins of the 18alpha H-oleana-9(11),12-diene type named glyyunnansapogenins G and H were isolated from the roots of GLYCYRRHIZA YUNNANENSIS Cheng f. et L. K. Tai. Their structures were elucidated as 18alpha H-oleana-9(11),12-diene-3beta,21alpha,29-triol and 18alpha H-3beta,21alpha-dihydroxyoleana-9(11),12-dien-29-oic acid, respectively, by spectroscopic methods. This is the first report of the occurrence of the 18alpha H series of oleana-9(11),12-diene compounds in nature.     

Two new taxane diterpenoids from the seeds of the Chinese yew, Taxus yunnanensis

A new taxoid and a taxinine analogue were isolated from the seeds of the Chinese yew, Taxus yunnanensis. The structures were established as 13 alpha-acetoxy-5 alpha-(3'-dimethylamino-3'-phenyl)-propionyloxy-11(15-->1)-abeotaxa- 4(20),11-diene-9 alpha, 10 beta-diol and 2 alpha-acetoxy-5 alpha-cinnamoyloxy-9 alpha, 10 beta-dihydroxy-taxa- 4(20),11-diene-13-one on the basis of 1D, 2D NMR, and MS spectral analysis.     

云南红豆杉抗肿瘤活性成分的研究

云南红豆杉(Taxus yunnanensis Cheng et L.K.Fu)树皮的乙醇提取物显示较强的抗肿瘤活性,从中分离得到8个紫杉烷类二萜及其生物碱。经光谱分析和化学反应鉴定7个已知物为taxinine E(1),taxinine J(2),1-acetoxy-5-deacetvl baccatin Ⅰ(4),baccatin Ⅲ(5),taxol(6),cephalomannine(7)和7-xylosyl-10-deacetyl taxol(8)。化合物3命名为云南红豆杉甲素(ymlnanxane),为一新的紫杉烷二萜化合物,其结构为taxa-4(20),11-diene-2α,5α,10β,14β-tetraol-2α,5α,10β-triacetate-14β-αmethyl-β-hydroxyl butyrate,并通过X-射线单晶衍射予以证实.经体外筛迭化合物3具有抗肿瘤活性。     

Taxumairol M: a new bicyclic taxoid from seeds of Taxus mairei.

In addition to taxol A (1), 10-deacetyltaxol A (2), 10-deacetyl-7-epi-taxol A (3), 10-deacetylbaccatin III (5), taxuspine Z, taxezopidine G, 5 alpha-cinnamoyloxy-9 alpha,10 beta,13 alpha-triacetoxytaxa-4(20)11-diene, taxinine J, and taxinine M, a new bicyclic taxoid named taxumairol M (4), has been isolated from the seeds of Taxus mairei. The structure of 4 was determined on the basis of spectral analysis.     

Two new sesquiterpene lactones from Montanoa tomentosa ssp. microcephala.

Two new sesquiterpene lactones: 8alpha-(4'-acetoxymethacryloyloxy)-3alpha,9beta-dihydroxy-1(10)E,4Z,11(13)-germacratrien-12,6alpha-olide (1) and 8alpha-(2'E)-(2'-acetoxymethyl-2'-butenoyloxy)-3alpha,9beta-dihydroxy-1(10)E,4Z,11(13)-germacratrien-12,6alphaolide (2), together with the known zoapatanolide A were isolated from the aerial parts of Montanoa tomentosa Cerv. in La Llave et Lex ssp. microcephala (Sch. Bip. In K. Koch) V.A. Funk (Asteraceae). The structures of all compounds were established on the basis of 1D, 2D NMR, and EIMS analysis.     

云南红豆杉中四个新紫杉烷类二萜化合物的分离和结构鉴定

自云南红豆杉(Taxus yunnanensis ChengetL.K.Fu)树皮的二氯甲烷提取部分又分离得到7个紫杉烷类二萜和生物碱,经光谱(IR,MS,¹HNMR,¹H-¹H’COSY,¹³C-¹HCOSY)解析推定4个新的紫杉烷类二萜涨化合物的结构为5-decinnamoyl-11-acetyl-19-hydroxyl taxagifine(I),2-deacetoxy-5.decinnamoyl taxinineJ(II),1-hydroxy-2,7,9-trideacetyl baccatinI(IV)和7-xyIosyl-10-deacetyl baccatinIII(VII),3个已知的紫杉烷类二苑和生物碱是5-decinnamoyI taxinineJ(III),7-xylosyl taxol(V)和7-xylosyl cephalomannine(VI),它们是首次从该植物中得到。     

Novel antimicrobial diterpenoids from Turraeanthus africanus

The dichloromethane-methanol (1/1) extract of the stem bark of Turraeanthus africanus (Meliaceae) showed remarkable antimicrobial activity against Cryptococcus neoformans, Staphylococcus aureus and methicillin-resistant S. aureus. Phytochemical investigation of this extract afforded six new diterpenoid derivatives, (+)-16-acetoxy-12,15-epoxylabda-8(17),12,14-triene ( 3), [16( E),12 S,15 R]-16-acetoxy-12,15-epoxy-15-isopropoxy- ent-labda-8(17),13(16)-diene (turraeanin A, 4), [16( E),12 R,15 S]-16-acetoxy-12,15-epoxy-15-isopropoxy- ent-labda-8(17),13(16)-diene (turraeanin B, 5), [16( E),12 S,15 R]-16-acetoxy-12,15-epoxy-15-methoxy- ent-labda-8(17),13(16)-diene (turraeanin C, 6), [16( E),12 R,15 S]-16-acetoxy-12,15-epoxy-15-methoxy- ent-labda-8(17),13(16)-diene (turraeanin D, 7) and (12 S,13 S,15 R)-12,15-epoxy-15-methoxy- ent-labd-8(17)-en-16-al (turraeanin E, 9) together with the known compounds, 15,16-epoxy- ent-labda-8(17),13(16),14-triene ( 1), (+)-pumiloxide ( 2), ent-labda-8(17),12 ( E)-diene-15,16-dial ( 8) and 16-acetoxy-12( R),15-epoxy-15beta-hydroxylabda-8(17),13 (16)-diene ( 10). Compound 10 was obtained as its acetoxy derivative ( 10a) and compound 11 was the product of hydrolysis of 6. Antimicrobial activity of the isolates was assayed and compounds 8, 9, 10a and 11 exhibited significant activities.     

Sesquiterpenes from Artemisia giraldii var. longipedunculata

A phytochemical investigation on the aerial parts of Artemisia giraldii var. longipedunculata led to the isolation of 10 known sesquiterpenes, including12-hydroxy-α-cyperone (1), 1β,6α-dihydroxyeudesma-4(15)-ene (2), carainterol A (3), oplodiol (4),douglanin (5), 1α-hydroxyisodauc-4-en-15-al (6), 3α,6α-dihydroxybisabola-4,10-diene (7), 4α,5β-dihydroxybisabola-2,10-diene(8), opposit-4(15)-ene-1β,7-diol (9), and saniculamoid D (10), respectively. Their structures were elucidated by analysis of the MS and NMR spectroscopic data and comparison with the literature. All the isolates were obtained from A. giraldii var. longipedunculata for the first time, and five of them were obtained from the genus Artemisia for the first time. Additionally, the ¹³C NMR data of 1 were fully assigned based on the 2D NMR data for the first time.     

人工栽培的南方红豆杉化学成分研究(III)

从人工栽培的南方红豆杉全株乙醇提取物的氯仿萃取部位通过反复硅胶和凝胶柱层析分离得到4个化合物，采用波谱解析(IR，ESI-MS，¹H NMR和¹³C NMR)等方法确定了其结构，4个化合物分别鉴定为taxamairin K (1), 2α,4α-dideacetoxy-7β-benzoyloxy-5β,20-epoxy-9α,10β,13α,15-tetrahydroxy-11(15→1)abeotaxa-11-ene (2), 7β-xylosyl-taxol (3), 10-deacetoxy-7-xylosyl-taxol (4)，其中化合物1为新化合物。     

Diterpenoids from the freshwater green algae Rhizoclonium hieroglyphicum with antibacterial activity

Three new isopimarane diterpenes 7β-hydroxy-19α-methylmalonyloxy-isopimara-8(14),15-diene (1), 7β-hydroxy-14-oxo-isopimara-8(9),15-dien-19oic acid (2), and 7β-hydroxy-14-oxo-19α-methylmalonyloxy-isopimara-9(11),15-diene (3) in addition to the known compounds isopimaric acid (4), 7oxo-13-epi-pimara-14,15-dien-18oic acid (5), 7oxo-13-epi-pimara-8,15-dien-18oic acid (6), and 6β-hydroxyisopimaric acid (7) were isolated from the hexane extract of Rhizoclonium hieroglyphicum. The structures of compounds 1-7 were established by 1D and 2D NMR techniques. The isolated diterpenoids were screened for antimicrobial activity against gram-positive and gram-negative bacteria and yeast strains.     

Four new minor taxanes from cell cultures of Taxus chinensis

Four new minor taxanes (1–4) have been isolated from Ts-19 cell cultures of Taxus chinensis together with five known taxanes (5–9) by silica gel chromatography combined with semi-preparative HPLC chromatography. On the basis of the analyses of the chemical and spectroscopic (IR, MS, 1D, and 2D NMR) data, the structures of new compounds were elucidated as 5α-hydroxy-2α,10β-diacetoxy-14β-(3-hydroxy-2-methyl-butyryl)oxytaxa-4(20),11-diene (1), 2α,5α,10β-triacetoxy-14β-(2-hydroxy-propionyl)oxytaxa-4(20),11-diene (2), 2α,5α,10β-triacetoxy-14β-(2-hydroxy-3-methyl-butyryl)oxytaxa-4(20),11-diene (3), and 2α-benzoxy-4α,9α,10β,13α-tetraacetoxytax-11-ene (4), respectively. Compounds 1–5 were pharmacologically evaluated for their cytotoxicities against five human cancer cell lines (HCT-8, Bel-7402, BGC-823, A549, and A2780) and their reversing activity towards multi-drug resistance A549/taxol tumor cell line, and the results showed that all of the tested compounds exhibited very low cytotoxicities, while compound 4 possessed twice the reversing activity as that of verapamil at 10 μM.     

Sesquiterpene lactone glycosides,eudesmanolides, and other constituents from Carpesium macrocephalum

Two new sesquiterpene lactone glycosides and two new eudesmanolides, along with twelve known compounds were isolated from seeds of Carpesium macrocephalum. The structures of these new compounds were elucidated as 2alpha- O-beta- D-glucopyranosyl-5alpha, 11alpha H-eudesma-4(15)-en-12,8beta-olide ( 1), 2alpha- O-beta- D-glucopyranosyl-5alpha H-eudesma-4(15),11(13)-dien-12,8beta-olide ( 2), 2alpha-acetoxy-5alpha-hydroxy-11alpha H-eudesma-4(15)-en-12,8beta-olide ( 3) and 2alpha,5alpha-dihydroxy-11alphaH-eudesma-4(15)-en-12,8beta-olide ( 4) by spectroscopic methods including 2D NMR techniques ( (1)H- (1)H COSY, (1)H- (1)H NOESY, HMQC, HMBC) and chemical transformations. Compounds 1, 6, 8, 9 and 10 exhibited moderate antibacterial activity, while compound 4 showed appreciable cytotoxic activity against cultured SMMC-7721 (human hepatoma cell).     

Two new dammarane triterpene glycosides from the rhizomes of Panax notoginseng

Two new dammarane triterpene glycosides named notoginsenosides Rw 1 (1) and Rw 2 (2) were isolated from the rhizomes of Panax notoginseng, together with 20 known compounds including protopanaxadiol (3), protopanaxatriol (4), ginsenosides Rb1 (5), Rd (6), Re (7), Rg1 (8), Rg2 (9), 20-(S)-Rg3 (10), 20-(R)-Rg(3) (11), Rh1 (12), Rh4 (13), Rf (14), 20-O-glucopyranosyl Rf (15), notoginsenosides R1 (16), R2 (17), T5 (18), S (19), T (20), and Fa (21), and koryoginsenoside R1 (22). Based on FABMS, HRFABMS, IR, (1)H, 13C, and 2D-NMR (HSQC, HMBC, and COSY) spectral data, the structures of the new compounds were elucidated as 6-O-beta-d-xylopyranosyl-20-O-beta-d-xylopyranosyl-(1 --> 6)-beta-d-glucopyranosyldammar-24-ene-3beta,6alpha,12beta,20(S)tetraol (1) and 6-O-beta-d-xylopyranosyl-(1 --> 2)-beta-d-glucopyranosyldammar-22-ene-(trans)-3beta,6alpha,12beta,20(S), 25-pentaol (2). Compounds 3, 4, 13, and 22 were isolated from P. notoginseng for the first time.     

Three novel bicyclic taxane diterpenoids with verticillene skeleton from the needles of Chinese yew, Taxus chinensis var. mairei.

Three novel bicyclic taxane diterpenoids with the verticillene skeleton were isolated from the needles of Chinese yew, Taxus chinensis var. mairei. Their structures were established as (3E,7E)-2 alpha, 10 beta, 13 alpha, 20-tetraacetoxy-5 alpha-hydroxy-3,8-secotaxa-3,7,11-trien-9-one (1), (3E,7E)-2 alpha, 5 alpha, 10 beta, 13 alpha-tetraacetoxy-20-hydroxy-3,8-secotaxa-3,7,11-trien-9-one (2), and (3E,7E)-10 beta, 13 alpha-diacetoxy-2 alpha, 5 alpha, 20-trihydroxy-3,8-secotaxa-3,7,11-trien-9-one (3) on the basis of 1D, 2D NMR and HR-MS spectroscopic analysis. Verticillene skeleton was considered as the biogenetic intermediate of taxane diterpenoids, isolation of bicyclic taxane diterpenoids with verticillene skeleton from this plant provides direct proof for this hypothesis.     

云南红豆杉中四个新紫杉烷类四环二萜成分的分离和鉴定

从云南红豆杉(Taxus yunnanensis ChengetL.K.Fu)树皮的二氯甲烷部分又分离得到四个新紫杉烷类四环二萜化合物,分别命名为taxayuntin A,B,C和D。应用¹HNMR,¹³CNMR,¹H-¹HCOSY,¹³C-¹HCOSY及¹³C-¹HCOLOC等方法进行结构测定,证明它们都有5/7/6三环稠合的基本骨架,并在C₄和C₅上连有环氧丙烷。     

构树叶的化学成分

为研究构树叶(Broussonetia papyrifera)的化学成分，用Diaion HP-20，Toyopearl HW-40C，Sephadex LH-20，silica gel等柱色谱方法进行分离，根据其理化性质和波谱数据鉴定化合物结构。分离得到了19个化合物，分别鉴定为芹菜素(1)，芹菜素-7-O-β-D-吡喃葡糖苷(2)，柯伊利素-7-O-β-D-吡喃葡糖苷(3)，芹菜素-7-O-β-D-吡喃葡糖醛酸苷(4)，牡荆素-7-O-β-D-吡喃葡糖苷(5)，木犀草素(6)，5,7,4′-三羟基-6-C-［a-L-鼠李糖(1→2)］-β-D-葡糖黄酮碳苷(7)，5,7,4′-三羟基-8-C-［α-L-鼠李糖(1→2)］-β-D-葡糖黄酮碳苷(8)，异牡荆素(9)，牡荆素(10)，苯甲酸苯甲酯-2,6-二-O-β-D-吡喃葡糖苷(11)，(2R,3R,5R,6S,9R)-3-羟基-5,6-环氧-β-紫罗兰醇-2-O-β-D-葡糖苷(12)，(2R,3R,5R,6S,9R)-3-羟基-5,6-环氧-乙酰-β-紫罗兰醇-2-O-β-D-葡糖苷(13)，ficustriol (14)，(6S,9S)-玫瑰花苷(15)，3β-羟基-5α,6α-环氧-β-紫罗兰酮-2α-O-β-D-葡糖苷(16)，icariside B₁ (17)，sammangaoside A (18)，3-羟基-5α,6α-环氧-β-紫罗兰酮(19)。化合物11、12、13为新化合物，其余化合物为首次从该属植物中分离得到。     

Three New Taxane Diterpenoids from the Seeds of the Chinese Yew,Taxus Chinensis var Mairei

Abstract

Three new taxoids were isolated from the seeds of the Chinese yew, Taxus chinensis var mairei, their structures were established as 9α,13α-diacetoxy-5α-cinnamoyloxy-11(15 → 1)-abeo-taxa-4(20), 11-diene-10β,15-diol, 2α,9α,10β-triacetoxy-taxa-4(20),11-diene-5α,13α-diol and 2α,7β,10β-triacetoxy-5α-cinnamyloxy-9α-hydroxy-taxa-4(20),11-diene-13-one on the basis of 1D, 2D NMR, and MS spectral analyses.     

东北红豆杉化学成分的分离与鉴定

目的对东北红豆杉(Taxus cuspidtaSibe.et Zucc.)的化学成分进行研究。方法采用硅胶柱色谱等方法进行分离纯化,根据理化性质和NMR波谱数据进行结构鉴定。结果分离得到8个化合物,分别鉴定为大黄素甲醚(physcion,1)、油酸甲酯(methyl oleate,2)、紫杉宁(taxinine,3)、5α-羟基-9α,10β,13α-三乙酰氧紫杉烷-4(20),11-二烯(5α-hydroxy-9α,10β,13α-triacetoxytaxa-4(20),11-diene,4)、云南紫杉宁C(taxuyunnanine C,5)、2-去乙酰氧-5α-羟基紫杉宁J(2-deacetoxydecin-namoyl taxinine J,6)、2-去乙酰氧紫杉宁J(2-deacetoxytaxinine J,7)、11-羟基-12-甲氧基松香烷-8,11,13-三烯-3,7-二酮(11-hydroxy-12-methoxyabieta-8,11,13-triene-3,7-dione,8)。结论化合物1、2为首次从红豆杉属植物中分离得到,化合物4、8为首次从该种植物中分离得到。