Two new dammarane-type triterpene saponins from red American ginseng

Two new dammarane-type triterpene saponins were isolated from the red American ginseng. The new saponins were named as pseudoginsenoside G₁ (1) and pseudoginsenoside G₂ (2). Their structures were elucidated by the combined analysis of NMR and mass spectrometry as 3-O-[β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl]-dammar-12-one-20S,24R-epoxy-3β,25-diol (pseudoginsenoside G₁) (1) and 3-O-[β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl]-dammar-12-one-20S,24S-epoxy-3β,25-diol (pseudoginsenoside G₂) (2).     

Two new triterpenoid saponins from ginseng medicinal fungal substance

Two new dammarane-type triterpenoid saponins, namely ginsenosides Rb₄ (1) and Rb₅ (2), were isolated from ginseng medicinal fungal substance. The structures of 1 and 2 were established as 3β,12β,20(S)-trihydroxydammar-24(25)-ene-3-O-[α-d-glucopyranosyl-(1→4)-β-d-glucopyranosyl-(1→2)-β-d-glucopyranosyl]-20-O-β-d-glucopyranoside and 3β,12β,20(S)-trihydroxydammar-24(25)-ene-3-O-[α-d-glucopyranosyl-(1→4)-α-d-glucopyranosyl-(1→4)-β-d-glucopyranosyl-(1→2)-β-d-glucopyranosyl]-20-O-β-d-glucopyranoside on the basis of spectroscopic analysis and chemical analysis, respectively.     

薤白甙J,K和L的结构

进一步用HPLC自小根蒜(Allium macrostemon Bunge)鳞茎中分得两种新的呋甾皂甙,薤白甙J(1)和薤白甙L(III),以及I的甲基化人工产物薤白甙K(II)。经过化学降解和光谱(¹H-NMR,¹³C-NMR和FAB-MS等)分析,确定其结构分别为:(25R)-26-O-β-D-吡喃葡萄糖基-22-羟基-5β-呋甾-2β,3β,26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(I);(25R)-26-O-β-D-吡喃葡萄糖基-22-甲氧基-5β-呋甾-2β,3β,26-.三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(II)和(25R)-26-O-β-D-吡喃葡萄糖基-5β-呋甾-20(22)-烯-26β,3β,26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(III)。     

扁果绞股蓝化学成分的研究

从扁果绞股蓝(Gynostemma compressum X. X. Chen et D. R. Liang)中分离出四个皂甙,经光谱及化学方法鉴定了它们的化学结构,分别命名为扁果绞股蓝皂甙Ⅰ～Ⅳ(gycomoside Ⅰ～Ⅳ),均为新化合物。     

薤白中两种新呋甾皂甙的结构

自中药薤白(Allium macrostemon Bunge)鳞茎中分得三种甾体皂甙。经过化学降解和光谱(UV、IR,MS,¹H-NMR,¹³C-NMR和FAB-MS)分析,鉴定其结构分别为(25R)-26-O-β-D-吡喃葡萄糖-5α-呋甾-20(22)-烯-3β,26-二醇-3-O-β-D-吡喃葡萄糖基(1→2)[β-D-吡喃葡萄糖基(1→3)]-β-D-吡喃葡萄精基(1→4)-β-D-吡喃半乳糖甙(Ⅰ),(25R)-26-O-β-D-吡喃葡萄糖基-5β-呋甾-20(22)-烯-3β,26-二醇-3-P-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅱ)和异菝契皂甙元-3-O-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅵ)。Ⅰ和Ⅱ为新的呋甾皂甙,分别命名为薤白甙戊和莲白甙己,初步药理实验测试二青均有较强的抑制ADP诱导的人血小板聚集作用。     

川续断中皂甙Ⅺ,Ⅻ和ⅩⅢ的结构研究

从川续断(Dipsacus asper Wall.)根的醇提物中得到三个微量新三萜皂甙(Ⅺ～ⅫⅠ),根据光谱分析和化学反应,其结构分别鉴定为3-O-[β-D-吡喃葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-常春藤皂甙元(Ⅺ)、Ⅺ的28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙( Ⅻ)和3-O-[β-D-吡喃木糖(1→4)-B-O-吡喃葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-B-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-齐墩果酸-28-O-β-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙(ⅫⅠ)。     

川产九节龙皂甙的化学研究

从川产九节龙(Ardisea pusilla A. DC)的正丁醇提取物中分离到两个三萜皂甙。经化学和光谱(IR,MS,¹HNRM,¹³CNMR和两种新的核磁技术)分析,两个化合物的结构分别鉴定为3-O-[α-L-吡喃鼠李糖(1→2)-β-D-吡喃葡萄糖(1→3)][B-D-吡喃葡萄糖(1→2)]-α-L-阿拉伯糖-西克拉敏A(Ⅰ)和3-O-[β-D-吡喃木糖(1→2)-B-D-吡喃葡萄糖-(1→4)][B-D-吡喃葡萄糖-(1→2)-β-D-吡喃葡萄糖(1→2)]-α-L-吡喃阿拉伯糖-西克拉敏A(Ⅱ)。二者均为新皂甙,依次命名为九节龙皂甙Ⅰ(ardipusilloside Ⅰ)和九节龙皂甙Ⅱ(ardipusillosidc Ⅱ)。     

灰毡毛忍冬化学成分的研究

从灰毡毛忍冬(Lonicera mocranthoide Hand. -Mazz.)花的乙醇提取物的正丁醇溶解部分分得三个常春藤皂甙元的双糖链甙,其中一个为已知化合物川续断皂甙乙(dipsacoside B,Ⅰ);另外两个为新化合物,分别命名为灰毡毛忍冬皂甙甲(macranthoidin A,Ⅱ)和灰毡毛忍冬皂甙(nmcranthoidin B,Ⅲ),两者的次级皂甙灰毡毛忍冬次皂甙甲(macranthoside A,Ⅱb)和灰毡毛忍冬次皂甙乙(macranthoside B,Ⅲb),亦未见报道。     

知母中呋甾皂甙的研究

自知母 Anemarrhena asphodeloides Bge.根茎的乙醇提取物中,经硅胶柱层析和制备型HPLC分得四种呋甾皂甙。用化学反应和波谱(IR,FAB-MS,EI-MS,¹HNMR,¹³CNMR,DEPT,一维多重接力CoSY,二维接力HOHAHA,¹H-¹H COSY,¹H-¹³C COSY和NOE差谱)解析,确定其结构为知母皂贰B(anemarsaponinB,I),(25S)-26-O-β-D-吡喃葡萄糖基-5β-呋甾-20(22)-烯-3β,26-二醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃哺葡萄糖甙(Ⅱ),(25S)-26-O-β-D-吡喃葡萄糖基-22-羟基-5β-呋甾-3β,26-二醉-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅲ),(25S)-26-O-β-D-吡喃葡萄糖基-22-甲氧基-5β-呋甾-3β,26-二醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅳ)。Ⅱ为一新的呋甾皂甙,命名为知母皂甙C;化合物Ⅳ为首次从知母中分离得到,命名为知母皂甙E。初步的药理实验显示,化合物1～Ⅳ均有一定的清除羟自由基的作用。     

New furostanol glycosides from the rhizomes of Dioscorea futschauensis R. Kunth

Two new furostanol glycosides, 26-O-β-D-glucopyranosyl-3β,26-dihydroxy-23(S)-methoxyl-25(R)-furosta-5,20(22)-dien-3-O-α-L-rhamnopyranosyl(1→2)-[β-D-glucopyranosyl(1→3)]-β-D-glucopyranoside (dioscoreside E, 1) and 26-O-β-D-glucopyranosyl-3β,26-dihydroxy-25(R)-furosta-5,20(22)-dien-3-O-α-L-rhamnopyranosyl(1→2)-[β-D-glucopyranosyl (1→3)]-β-D-glucopyranoside (prtotogracillin, 2), together with 11 known furostanol glycosides were isolated from the rhizomes of Dioscorea futshauensis R. Kunth. Their structures were elucidated on the basis of spectroscopic analysis (NMR and FABMS). Their anti-fungal activity against the plant pathogenic fungus Pyricularia oryzae and cytotoxic activity on K562 cancer cell line were evaluated in vitro.     

合欢皂苷J20的结构鉴定

目的:研究合欢皮的化学成分及活性。方法:用现代色谱法分离合欢皮皂苷,用化学和现代波谱法,主要是二维核磁共振技术鉴定结构。结果及结论:分离并鉴定了一个新三萜皂苷,结构为3-O-[β-D-吡喃木糖基-(1→2)-α-L-吡喃阿拉伯糖基-(1→6)-β-D-吡喃葡糖基]-21-O-｛(6S)-2-反式-2-羟甲基-6-甲基-6-O-β-D-吡喃木糖基-2,7-辛二烯酰基｝金合欢酸28-O-β-D-吡喃葡糖基-(1→3)-[α-L-呋喃阿拉伯糖基-(1→4)]-α-L-吡喃鼠李糖基-(1→2)-β-D-吡喃葡糖基酯,命名为合欢皂苷J₂₀(JulibrosideJ₂₀)。     

Quinquenoside L9 from Leaves and Stems of Panax Quinquefolium L

Abstract

During additional chemical investigation on the saponin composition of leaves and stems of Panax quinquefolium L, a new minor dammarane saponin, quinquenoside L₉ (1) has been obtained. By means of physico-chemical evidences and spectral analysis, its structure was elucidated as 6-O-[α-L-rhamnopyranosyl-(1–2)-β-D-glucopyranosyl]-dammara-3β,6β,12β,20(S),24ζ,25-hexaol (1).     

A pair of isomeric saponins with cytotoxicity from Albizzia julibrissin

Two new saponins have been isolated from the stem barks of Albizzia julibrissin Durazz, and their structures identified as 3-O-[β-d-xylopyranosyl-(1 → 2)-β-d-fucopyranosyl-(1 → 6)-β-d-2-deoxy-2-acetoamidoglucopyranosyl]-21-O-{(6S)-2- trans -2-hydroxymethyl-6-methyl-6-O-[4-O-((6S )-2- trans -2-hydroxymethyl-6-hydroxy-6-methyl-2,7-octadienoyl)-β-d-quinovopyranosyl]-2,7-octadienoyl}-acacic acid-28-O-β-d-glucopyranosyl-(1 → 3)-[α-l-arabinofuranosyl-(1 → 4)]-α-l-rhamnopyranosyl-(1 → 2)-β-d-glucopyranosyl ester (1) and 3-O-[β-d-xylopyranosyl-(1 → 2)-β-d-fucopyranosyl-(1 → 6)-β-d-2-deoxy-2-acetoamidoglucopyranosyl]-21-O-{(6S)-2-trans-2-hydroxymethyl-6-methyl-6-O-[3-O-((6S)-2-trans-2-hydroxymethyl-6-hydroxy-6-methyl-2,7-octadienoyl)-β-d-quinovopyranosyl]-2,7-octadienoyl}acacic acid 28-O-β-d-glucopyranosyl-(1 → 3)-[α-l-arabinofuranosyl-(1 → 4)]-α-l-rhamnopyranosyl-(1 → 2)-β-d-glucopyranosyl ester (2), based on chemical and spectral evidences, named as julibroside J₁₉ and julibroside J₁₈, respectively. Both compounds show significant inhibition action against HeLa, Bel-7402 and MDA-MB-435 cancer cell lines in vitro.     

New cycloartane glycosides from Camptosorus sibiricus Rupr

Three new cycloartane glycosides were isolated from the whole herbs of Camptosorus sibiricus Rupr. By means of chemical and spectroscopic methods (IR, 1D, and 2D NMR, HR-MS, ESI-MS), the structures were established as (24R)-3β,7β,24,25, 30-pentahydroxycycloartane-3-O-β-d-glucopyranosyl-(1 → 4)-[α-l-arabinopyranosyl-(1 → 2)-β-d-glucopyranosyl]-24-O-β-d-glucopyranoside (1), (24R)-3β,7β,24,25,30-pentahydroxycycloartane-3-O-β-d-glucopyranosyl-(1 → 4)-[β-d-galactopyranosyl-(1 → 2)-β-d-glucopyranosyl]-24-O-β-d-glucopyranoside (2), (24R)-3β,7β,24,25,30-pentahydroxycycloartane-30-O-coumaroyl-3-O-β-d-glucopyranosyl-24-O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside (3). At the same time, the new compounds were tested for their cytotoxicities in vitro against human tumor cell lines (A375-S2, Hela) using MTT method.     

太白木忽木根皮中三萜皂甙成分研究

从太白木忽木(Aralia taibaiensis Z.Z.WangetH.C.Zheng)根皮中首次分离到四个三萜皂甙,根据理化性质和光谱数据,分别鉴定为齐墩果酸-3-O-[β-D-吡喃木糖(1→2)][β-D-吡喃葡萄糖(1→3)]-β-D-吡喃葡萄糖醛酸甙(1),tarasaponinV(2),3-O-｛β-D-吡喃木糖(1→2)[β-D-吡喃葡萄糖(1→3)]-β-D-吡喃葡萄糖醛酸乙酯｝-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(3)和3-O-｛β-D-吡喃木糖(1→2)[β-D-吡喃葡萄糖(1→3)]-β-D-吡喃葡萄糖醛酸丁酯｝-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(4)。1为新天然产物,3和4为新化合物,分别命名为太白木忽木皂甙VI(taibaienosideVI)、太白木忽木皂甙VII(taibaienoside VII)和太白木忽木皂甙VII(taibaienoside VII)。     

黑柴胡中新三萜皂甙的结构鉴定

从黑柴胡(Bupleurum smithii Wolff)根中分离出10个化合物,均为首次由该植物中获得。其中二个新三萜皂甙,即柴胡皂甙k和l(saikosaponin k and l),其结构经紫外、红外、核磁共振氢谱,碳谱和质谱等波谱测定和解析,分别确定为3β,16β,23,28-四羟基齐墩果烷-11,13(18)-二烯-3-O-β-D-吡喃木糖基-(1→2)-β-D-吡喃葡萄糖基-(1→3)-β-D-吡喃呋糖甙和3β,16α,23,28,30-五羟基齐墩果烷-11,13(18)-二烯-3-O-β-D-吡喃葡萄糖基-(1→3)-β-D-吡喃呋糖甙。     

Three triterpenoid saponins acylated with monoterpenic acid from Gymnocladus chinensis

A new triterpenoid saponin acylated with monoterpenic acid, together with two known triterpenoid saponins, has been isolated from the fruit of Gymnocladus chinensis Baill. Their structures were elucidated as 2β,23-dihydroxy-3-O-α-L-rhamnopyranosyl-21-O-{(6S)-2-trans-2,6-dimethyl-6-O-[3-O-(β-D-glucopyranosyl)-4-O-((6S)-2-trans-2,6-dimethyl-6-hydroxy-2,7-octadienoyl)-β-L-arabinopyranosyl]-2,7-octadienoyl}-acacic acid 28-O-β-D-xylopyranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 4)-α-L-rhamnopyranosyl-(1 → 2)-[α-L-rhamnopyranosyl-(1 → 6)]-β-D-glucopyranosyl ester (1), gymnocladus saponin E (2), and gymnocladus saponin F₂ (3).     

Four new triterpenoid glycosides from the seed residue of Hippophae rhamnoides subsp. sinensis

Four new triterpenoid saponins (1–4) were isolated from the seed residue of Hippophae rhamnoides subsp. sinensis, named 3-O-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl-(1 → 3)]-[α-l-rhamnopyranosyl-(1 → 2)]-α-l-arabinopyranosyl-13-ene-19-one-28-oic acid 28-O-β-d-glucopyranosyl ester (1), 3-O-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl-(1 → 3)]-[α-l-rhamnopyranosyl-(1 → 2)]-α-l-arabinopyranosyl-13-ene-19-one-30-hydroxyolean-28-oic acid 28-O-β-d-glucopyranosyl ester (2), 3-O-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl-(1 → 3)]-[α-l-rhamnopyranosyl-(1 → 2)]-β-d-glucopyranosyl-13-ene-19-one-28-oic acid 28-O-β-d-glucopyranosyl ester (3), and 3-O-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl-(1 → 3)]-[α-l-rhamnopyranosyl-(1 → 2)]-β-d-glucopyranosyl-13-ene-19-one-30-hydroxyolean-28-oic acid 28-O-β-d-glucopyranosyl ester (4), and their structures were elucidated on the basis of spectroscopic and chemical methods.     

刺人参甙O和P的分离与结构鉴定

自刺人参(Oplopanax elatus Nakai)叶中分离出两种新皂甙,分别命名为刺人参甙O和P。根据理化常数和光谱数据,甙O的结构鉴定为:3-表齐墩果酸-28-氧-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖甙(1);甙P的结构为3-氧-β-D-吡喃葡萄糖基白桦脂酸-28-氧-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖甙(2)。     

用核磁共振新技术测定川续断皂甙F和H1两个新皂甙的结构及光谱规律研究

从川续断(Dipsacus asperoides c．Y．cheng et T．M．Ai)根部的乙醇提取物中得到二个新三萜皂甙，命名为川续断皂甙(asperosaponins)F和H₁。川续断皂甙F(I)是含六个糖的皂甙，川续断皂甙H₁(II)是含八个糖的皂甙。运用化学方法及光谱(¹HNMR，¹³CNMR，¹H-¹H COSY，——维多重接力COSY，选择性远程DEPT和三重共振NOE差谱)解析，鉴定其结构分别为3-O-[β-D-吡喃木糖(1→4)-β-D-吡哺葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-β-D-吡喃半乳糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-常春藤皂甙元(I)和3-0-[β-D-吡喃木糖(1→4)-β-D-吡喃葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-β-D-吡喃半乳糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L一吡喃阿拉伯糖-常春藤皂甙元-28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙(II)。并总结出一些光谱方面的变化规律，可用于糖的鉴定，以及构型、糖链的连接顺序和糖与甙元之间的连接位置的说明。