Three new dammarane glycosides from heat processed ginseng

Three new dammarane glycosides were isolated from the processed ginseng (SG; Sun Ginseng). Their structure were determined to be 3beta,12beta-dihydroxydammar-20(21),24-diene-3-O-beta-D-glucopyranosyl(1 --> 2)-beta-D-glucopyranoside; 3beta,12beta-dihydroxydammar-20(21),24-diene-3-O-beta-D- glucopyranoside and 3beta,6alpha,12beta-trihydroxydammar-20(21),24-diene-6-O-beta-D-glucopyranoside based on spectroscopic evidences. The compounds were named as ginsenoside Rk1, Rk2, and Rk3 respectively.     

秦岭珠子参叶的达玛烷型皂甙的进一步研究

前已报道秦岭产珠子参(Panax japonicus var.mojor (Burk.) Wu et Feng)叶的九个达玛烷型皂甙成分。本文继续报告得自珠子参叶的另外两个新的同类皂甙成分。珠子参甙F_σ(Ⅰ) 由甲醇中得白色粉末,分子式:C_(48)H_(82)O_(19);正、反相薄层层析示为单一斑点;PPC检查Ⅰ的酸水解物中有葡萄糖和鼠李糖存在:FAB-MS给出分子离子峰m/z 985 (M Na)~ 及碎片峰716(M-162-2H_2O 2H)~ ,619(M-162-146-2H_2O H)~ ,439(M-2×162-146-3H_2O 2H)~ ,说明Ⅰ中含有二个葡萄糖和一个鼠李糖。     

Minor Saponins from the Leaves of Panax ginseng C.A. Meyer

<正> Five minor compounds isolated from the leaves of Panax ginseng C. A. Meyer were characterized as 20(R)-protopanaxatriol (1), daucosterin (2), 3β, 12β-dihydroxy-dammar-20 (22), 24-diene-3-O-β-D-glucopyranoside (3), 20 (R)-protopanaxadiol-3-O-β-D-glucopyranoside (4) and ginsenoside-Rh_2 (5), respectively, on the basis of spectral analyses and chemical evidence. The two new saponins, 3 and 4, were named as ginsenoside-Rh_3 and 20(R)-ginsenoside-Rh_2.Nine other major saponins obtained simultaneously were identical with ginsenoside-Rh_1(6),-Rg_3 (7), -Rg_2 (8), -Rg_1 (9),-Re(10),-Rd (11), -Rc (12), -Rb_2(13) and Rb_1 (14), respectively.     

A New Minor Saponin from the Leaves of Panax ginseng

Seventeen compounds were isolated from the leaves of PANAX GINSENG C. A. Meyer. Among them, a new minor saponin was established as 3beta,6alpha,12beta-trihydroxy-dammar-20(22), 24-diene-6- O-alpha- L-rhamno-pyranosyl-(1-->2)-beta- D-glucopyranoside ( 2). Fourteen compounds were identified as 20( R)-protopanaxadiol ( 1), 20( R)-protopanaxatriol, ginsenoside-Rh (3), 20( R)-ginsenoside-Rh (2), 20( S)-ginsenoside-Rh (2), ginsenoside-Rh (1), -Rg (3), -Rg (2), -Rg (1), -Re, -Rd, -Rc, -Rb (2), -Rb (1); the others are still under investigation.     

西洋参茎叶总皂苷碱降解成分西洋参茎叶总皂苷碱降解成分

目的研究西洋参茎叶总皂苷碱降解成分。方法采用硅胶柱色谱并结合HPLC进行分离纯化，通过波谱分析鉴定化合物的结构。结果从西洋参茎叶总皂苷碱降解产物中分离得到9种成分，分别鉴定为：20(S)-原人参二醇(I)，20(S)-达玛-25(26)-烯-3β,12β,20-三醇(II)，24(R)-ocotillol (III)，20(S)-原人参三醇(IV)，20(S)-达玛-25(26)-烯-3β,6α,12β,20-四醇(V)，达玛-20(21),24-二烯-3β,12β-二醇(VI)，达玛-20(21),24-二烯-3β,6α,12β-三醇(VII)，20(S),24(S)-达玛-25(26)-烯-3β,6α,12β,20,24-五醇(VIII)，20(S)-达玛-23-烯-25-过氧羟基-3β,6α,12β,20-四醇(IX)。结论碱降解20位S构型未改变。V，VII，VIII，IX为4个新化合物，并利用2D-NMR技术对新化合物的氢和碳的化学位移进行了归属。其中I对HCT-8人结肠癌细胞具有较强的细胞毒活性。     

Two new triterpenoid saponins from Sarcandra glabra

Two new triterpenoid saponins, named sarcandroside A and B, have been isolated from Sarcandra glabra (Thunb) Nakai. Their structures have been established as 3beta,19alpha,20beta-trihydroxyurs-11,13 (18)-diene-28,20beta-lactone-3-O-beta-D-glucopyranosyl (1 --> 3)-[alpha-L-rhamnopyranosyl(1 --> 2)]-beta-D-xylopyranoside (1) and 3-O-beta-D-glucopyranosyl (1 --> 3)-[alpha-L-rhamnopyranosyl(1 --> 2)]-beta-D-xylopyranosyl-pomolic acid 28-O-beta-D-glucopyranosyl ester (2) by means of spectral and chemical methods.     

Isoginsenoside-Rh3, a new triterpenoid saponin from the fruits of Panax ginseng C. A. Mey

A new dammarane-type triterpene monoglucoside, named isoginsenoside-Rh(3), has been isolated from the fruits of Panax ginseng C. A. Mey, together with eight known analogs, ginsenoside-Rb(1), -Rb(2), -Rc, -Rd, -Re, -Rg(1), -Rh(1), -Rh(2). On the basis of chemical and physicochemical evidence, the structure of isoginsenoside-Rh(3) has been elucidated as 3-O-beta--glucopyranosyl-dammarane-(E)-20(22),24-diene-3beta,12beta-diol (1).     

Four new dammarane-type triterpene saponins from the stems and leaves of Panax ginseng and their cytotoxicity on HL-60 cells

Four new triterpene saponins, ginsenosides Rh(14)-Rh(17)(1- 4), along with two known compounds, 20(S)-ginsenoside Rg? and dammar-(E)-20(22),24-diene-3 β,6 α,12 β-triol, were isolated from the stems and leaves of Panax ginseng. The structures of the new compounds were elucidated as 3 β,6 α,12 β,24 ξ-tetrahydroxy-dammar-(E)-20(22),25-diene 6- O- α- L-rhamnopyranosyl-(1?→?2)- β-D-glucopyranoside (1), 3 β,12 β,24 ξ-trihydroxy-dammar-(E)-20(22),25-diene 3- O- β- D-glucopyranosyl-(1?→?2)- β-D-glucopyranoside (2), 3 β,6 α,12 β-trihydroxy-dammar-(E)-20(22),24-diene 3-O-β-D-glucopyranoside (3), and 3-oxo-6 α,12 β,20(S)-trihydroxy-dammar-24-ene 6-O-α-L-rhamnopyranosyl-(1?→?2)-β-D-glucopyranoside (4) by means of extensive spectroscopic and chemical methods, respectively. The isolated compounds were tested for IN VITRO cytotoxicity against HL-60 cells.     

Ginsenoside Rg5, a genuine dammarane glycoside from Korean red ginseng

A genuine dammarane glycoside, named ginsenoside Rg₅, has been isolated by repeated column chromatography and preparative HPLC from the MeOH extract of Korean red ginseng (Panax ginseng C.A. Meyer). The chemical structure of ginsenoside Rg₅ was determined as 3-O-[β-D-glucopyranosyl (1→2)-β-D-glucopyranosyl] dammar-20(22),24-diene-3β,12β-diol by spectral and chemical methods. The stereostructure of a double bond at C-20(22) of ginsenoside Rg₅ was characterized as (E) from the chemical shift of C-21 in the¹³C-NMR and a NOESY experiment in the¹H-NMR.     

薤白中两种新甾体皂甙成分

从中药薤白(Allium macrostemon Bunge)鳞茎中分得两种流的甾体皂甙,薤白甙甲(macrostemonoside A,1)和薤白甙丁(macrostemonoside D,2),通过光谱(IR,MS,¹HNMR,¹³CNMR,¹H-¹H COSY和NOESY等)分析和衍生化研究,分别确定为:tigogenin-3-O-β-D-glucopyranosyl(1→2)[β-D-glucopyranosyl(1→3)]-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside(1)和tigotenin-3-O-β-D-glucopyranosyl(1→2)[β-D-glucopyranosyl(1→3)(6-O-acetyl-β-D-glucopyranosyl)](1→4)-β-D-galactopyranoside(2)。     

The active constituents from Gualou-xiebai-baijiu-tang part I: active saponins

Two new steroidal saponins and a new triterpenoidal saponin, together with nine known steroidal saponins, were isolated from "Gualou-xiebai-baijiu-tang" consisting of Fructus trichosanthis and Bulbus allii macrostemi. The structures of the three new compounds were determined as 3-O-beta-D-galactopyranosyl-hederagenin 28-O-beta-D-xylopyranosyl (1-->6)-beta-D-galactopyranosyl ester (1), spirost 25(27)-ene-2beta,3beta-diol-3-O-beta-D-glucopyranosyl (1-->2)-beta-D-galactopyranoside (2) and 26-O-beta-D-glucopyranosyl-22alpha-hydroxy-5beta-furost-25(27)-ene-1beta,3beta,6beta,26-tetraol-3-O-beta-D-galactopyranoside (3), respectively, by means of chemical evidences and spectral analysis.     

Cytotoxic ergosterols from Paecilomyces sp. J300

Seven ergosterol derivatives (1-7) were isolated from silkworm larvae infected with Paecilomyces sp. J300. On the basis of spectroscopic means, their structures have been elucidated as 3beta,5alpha-dihydroxy-ergosta-7,22-diene (1), 5alpha,6alpha-epoxy-(22E,24R)-ergosta-8(14), 22-diene-3beta, 7alpha-diol (2), 5alpha,6alpha-epoxy-(22E,24R)-ergosta-8,22-diene-3beta,7alpha-diol (3), ergosta-4,6,8(14),22-tetraene-3-one (4), ergosterol (5), ergosterol endoperoxide (6), 3beta,5alpha-dihydroxy-6beta-methoxyergosta-7,22-diene (7). Compounds 3-7 showed moderate cytotoxicity against five tumor cells.     

薤中抗凝和抗癌活性成分的结构鉴定

从百合科葱属植物薤(Alium chinense)鳞茎的抗凝和抗癌活性部位中,分离得到了6个化合物。经过化学方法和光谱分析(IR,EI-MS,¹HNMR,¹³HNMR,¹H-¹HCOSY,HMBC,HMQC和NOESY谱),鉴定它们的结构分别为(25R,S)-5α-spirostane-3β-ol 3-O-｛β-D-glucopyranosyl-(1→2)-[β-D-glucopyra-nosyl-(1→3)]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside｝(1),(25R,S)-5α-spirostane-3β-ol 3-O-｛β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)](6-acetyl-β-D-glucopyranosyl)-(1→4)-β-D-galac-topyranoside｝(2),(25R,S)-5α-spirostane-2α,3β-diol3-O-｛β-D-glucopyranosyl-(1→2)-O-β-D-glucopyra-nosyl-(1→4)-β-D-galactopyranoside｝(3),(25S)-24-O-β-D-glucopyranosyl 3β,24β-dihydroxy-5α-spirost-3-O-α-arabinopyranosyl-(1→6)-β-D-glucopyranoside(4),chinenosideI(5)及2,3,4,9-tetrahydro-1-methyl-1H-pyrido[3,4-b]indole-3-carboxylicacid(6)。化合物4为一新的甾体皂甙,命名为chinenosideVI。化合物1～3为3对甾体皂甙差向异构体。其中,化合物2的25S型异构体为首次报道;25R型异构体和化合物6为首次从本种植物中分得。此外,通过NOESY谱还首次确定了化合物6的相对构型,并对其C和H信号进行了确切归属。     

知母皂甙E1和E2

应用硅胶柱色谱、高效液相色谱等分离手段,从中药知母(Anemarrhena asphodeloides Bge.)分离得到2种新的呋甾皂甙,经光谱(IR,ESI MS,¹HNMR,¹³HNMR)分析和化学反应,鉴定其结构分别是:(25S)-26-O-β-D-吡喃葡萄糖基-22-羟基-5-β-呋甾-3β,15α,26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(1),(25S)-26-O-β-D-吡喃葡萄糖基-22-甲氧基-5β-呋甾-3β,15α,26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(2)。(1)是新化合物,命名为知母皂甙E1;(2)是(1)的甲醚化人工产物,命名为知母皂甙E2。对知母皂甙-I(A)的结构分析作了简单说明。     

东北刺人参叶中四种新三萜皂苷的分离与结构鉴定

目的研究东北刺人参的三萜皂苷化学成分。方法采用大孔树脂、硅胶、ODS柱色谱分离纯化，经理化常数、光谱学方法鉴定结构。结果分离得到了4个新三萜皂苷，其结构分别鉴定为3-O-β-D-吡喃葡糖基3β，23-二羟基羽扇豆-20(29)-烯-28-酸-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡糖基(1→6)-β-D-吡喃葡糖苷(1);3-O-β-D-吡喃葡糖基常春藤皂苷元-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡糖基(1→6)-β-D-吡喃葡糖苷(2);3-O-β-D-吡喃葡糖基3β-羟基齐墩果-9(11)，12-二烯-28-酸-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡糖基(1→6)-β-D-吡喃葡糖苷(3);3α-羟基齐墩果-12-烯-23，28-二酸-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡糖基(1→6)-β-D-吡喃葡糖苷(4)。结论化合物1～4均为新三萜皂苷，首次从东北刺人参叶中分得。     

Ginsenoside Rf2, a new dammarane glycoside from Korean red ginseng (Panax ginseng)

A new dammarane glycoside named ginsenoside Rf₂ has been isolated from Korean red ginseng (Panax ginseng) and its chemical structure has been elucidated as 6-O-[α-L-rhamnopyranosyl (1→2) β-D-glucopyranosyl]dammarane-3β, 6α, 12β, 20(R), 25-pentol by chemical and spectral methods.     

New furostanol saponins from the bulbs of Allium macrostemon Bunge and their cytotoxic activity

Four new furostanol saponins, named as macrostemonoside O, macrostemonoside P, macrostemonoside Q and macrostemonoside R, along with five known compounds, were isolated from the dried bulbs of Allium macrostemon Bunge. The structures of these new compounds were established by the spectral data elucidation (IR, ESIMS, 1D and 2D NMR) as 26-O-beta-D-glucopyranosyl-22-hydroxyl-5beta-furost-25 (27)-ene-3beta, 26-diol-3-O-beta-D-glucopyranosyl (1-->2)-beta-D-galactopyranoside (macrostemonoside O), (25R)-26-O-beta-D-glucopyranosyl-22-hydroxyl-5beta-furost-1beta, 3beta, 26-triol-3- O-beta-D-glucopyranosyl (1-->2)-beta-D-galactopyranoside (macrostemonoside P), (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5beta-furost-1alpha, 2beta, 3beta, 26-tetraol-3-O-beta-D-glucopyranosyl (1-->2)-beta-D-galactopyranoside (macrostemonoside Q) and (25R)-26-O-beta-D-glucopyranosyl-22-hydroxyl-5beta-furost-2alpha, 3beta, 26-triol-3-O-beta-D-glucopyranosyl (1-->2) [beta-D-glucopyranosyl (1-->3)]-beta-D-glucopyranosyl (1-->4)-beta-D-galactopyranoside (macrostemonoside R), respectively. Their cytotoxic activities on several cancer cell lines including solid tumor (HepG2, MCF-7, NCI-H460 and SF-268) and drug resistant tumor (R-HepG2) were investigated and five compounds showed diverse cytotoxity to these cancer cell lines which suggest that they might be used as potential leading compounds to cure cancer diseases.     

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.     

Four new glycosides from Pleurospermum franchetianum

Four new glycosides, pleurofranosides I-IV, together with eight known compounds were isolated from the whole plants of Pleurospermum franchetianum Hemsl. Based on the spectral data and chemical evidence, the structures of pleurofranosides 1, II, III and IV were elucidated to be 16beta, 21beta, 23, 28-tetrahydroxyolean-12-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-glucopyranoside, 13beta, 28-epoxy-16beta, 23-dihydroxyolean-11-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-glucopyranosyl-(1 --> 2)]-beta-D-fucopyranoside, 13beta, 28-epoxy-16beta, 23-dihydroxyolean-11-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-fucopyranosyl-(1 --> 2)]-beta-D-glucopyranoside and 12beta, 28-epoxy-16beta, 23-dihydroxyolean-11-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 3)-[beta-D-glucopyranosyl-(1 --> 2)]-beta-D-glucopyranoside. The known compounds identified were octadecyl caprate, beta-sitosterol, (22E, 20S, 24R)-5alpha, 8alpha-epidioxy-ergosta-6, 22-dien-3-beta-ol, daucosterol, alpha-spinasterol-3-O-beta-D-glucopyranoside, quercetin-3, 7-di-O-beta-D-glucopyranoside, kaempferol-3, 7-di-O-alpha-L-rhamnopyranoside and kaempferol-3-O-beta-D-glucopyranosyl-7-O-alpha-L-rhamnopyranoside, respectively.     

Anticomplement activities of oleanolic acid monodesmosides and bisdesmosides isolated fromTiarella polyphylla

Seven known oleanolic acid glycosides (1-7) were isolated from the MeOH extract of Tiarella polyphylla. The structures were identified to be 3-O-(beta-D-glucopyranosyl) oleanolic acid (1), 3-O-[beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl] oleanolic acid (2), 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl] oleanolic acid (3), 3-O-[beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester (4), 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester (5), 3-O-[a-L-rhamnopyranosyl-(1-->3)-beta-D-glucuronopyranosyl] oleanolic acid (6), and 3-O-[alpha-L-rhamnopyranosyl-(1-->3)-beta-D-glucuronopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester (7) on the basis of physicochemical and spectral data. These triterpene glycosides were tested for the anticomplement activity and hemolytic activity. Bisdesmosidic saponins, 4, 5, and 7, showed anticomplement activity; in contrast, monodesmosidic saponins, 1-3, and 6, showed direct hemolytic activity. Methyl esterified monodesmosidic saponins showed anticomplement activity at a low concentration and hemolytic activity at a high concentration.