The Synthesis of Gracillin and Dioscin: Two Typical Representatives of Spirostanol Glycosides

Two spirostanol saponins (gracillin and dioscin) which have the typical sugar moieties were synthesized facilely by a general approach.

A New Spirostanol Saponin from Dioscorea futshauensis

A new spirostanol saponin presenting strong activity of inducing morphological deformation of Pyricularia oryzae mycelia was isolated from Dioscorea futshauensis R. Kunth by bioactivity-guided fractionation. The structure was established as (25S)-spirost-5-en-3 beta, 27-diol-3-O- [alpha -L-rhamnopyranosyl (1 -->2)-beta -D glucopyranosyl (1 -->3)]-beta -D-glucopyranoside on the basis of chemical evidences and spectral analysis, especially by 2D-NMR techniques.

New Spirostanol Sulfonate from the Rhizomes of Helleborus thibetanus(Ranunculaceae)

A new spirostanol sulfonate, spirost-5,25（27）-dien-1β,3β-diol 1-sulfonate（1）, was isolated from the rhizomes of Helleborus thibetanus（Ranunculaceae）, and the structure was identified on the basis of a detailed spectroscopic analyses, including 2D NMR spectrometry, IR and HRESI-MS.

A new spirostanol saponin from the rhizomes of Paris mairei

A new spirostanol steroidal saponin, named maireioside A （1）, together with three known steroidal saponins, hypoglaucin G （2）, parisaponin I （3）, and diosgenin-3-O-α-L-rhamnopyranosyl （1→4）-[α-L-rhamnopyranosyl （1→2）]-β-D-glucopyranoside （4）, were isolated from the rhizomes of Paris mairei. The structure elucidation was accomplished by 1D and 2D NMR methods, HR-ESI-MS, and hydrolysis. C 2009 Qiang Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Two New Highly Oxygenated Spirostanol Saponins from Paris polyphylla var.stenophylla

Phytochemical investigation of the rhizomes of Paris polyphylla var.stenophylla led to the isolation of two new highly oxygenated spirostanol saponins,named paristenosides A(1)and B(2),together with seven known compounds.Their structures were established mainly on the base of NMR spectroscopic techniques and mass spectrometry,as well as chemical methods.In addition,the cytotoxicity of the two new saponins was tested.Graphical Abstract Two new highly oxygenated spirostanol saponins,paristenosides A(1)and B(2),were isolated from the rhizomes of Paris polyphylla var.stenophylla.Their structures were established mainly based on NMR spectroscopic techniques and mass spectrometry,as well as chemical methods.

An Efficient Way for Glycosylation of Spirostanol

Using thioglycosides as donors, trimethylsilyl trifluoromethanesulfonate (TMSOTf) and N-iodosuccinimide(NIS) as promoter, a modified procedure for the glycosylation of spirostanol was developed. A series of saponins were synthesized in mild condition with excellent yields.

Separation and Bio-activities of Spirostanol Saponin from Tribulus terrestris

Gross saponins of Tribulus terrestris（GSTT） have exact effect on cardiovascular and cerebrovascular diseases.But as a mixture,the specific efficient component of GSTT is still unknown.Nine monomers of spirostanol saponins were isolated and idendified as JA―JI（named transitorily） by means of NMR spectrometry.After bio-activity screening on them,we defined that monomers tigogenin 3-O-β-D-xylopyranosyl（1→2）-[β-D-xylopyranosyl（1→3）]-β-D-glucopyranosyl（1→4）-[α-L-rhamnopyranosyl（1→2）]-β-D-galactopyranoside（compound JB） and hecogenin3-O-β-D-glucopyranosyl（1→4）-β-D-galactopyranoside（compound JG） have cytoprotective bio-activity.Compound JB display effective dose in 10-8 and 10-9 mol/L,and JG in 10-6―10-9 mol/L.Survival rate,lactate dehydrogenase（LDH） and apoptosis also show that JB（at dose 10-8,10-9 and 10-10 mol/L） can protect myocardial injury caused by hypoxia/reoxygenation（H/R）.While morphology change also shows JG has cytoprotective bio-activity.

Two New Spirostanol Steroidal Sapogenins from Fermented Leaves of Agave americana

Two new spirostanol sapogenins named agavegenin A and B were isolated from the fermented leaves of Agave americana L. Their structures were elucidated as (23S, 25R)-5a- spirostan-3b, 6a, 11a, 23-tetraol (1) and (23S, 25S)-5a-spirostan-3b, 23, 27-triol (2) by spectral methods.

A Facile Glycosylation of Spirostanol Catalyzed by Cadmium Carbonate

A facile glycosylation for the synthesis of spirostanol glycosides was reported. Using cadmium carbonate as a catalyst in CH3CN, a series of saponins was synthesized efficiently in a satisfactory yield.

TWO MINOR SPIROSTANOL GLYCOSIDES FROM SMILAX MENISPERMOIDE

Two minor steroidal saponins were isolated from the roots of Smilax menispermoidea.One of them is new and its structure was established as(25S) spirost-5-en-3β,17α,27-triol-3-O-[α-L-rhamnopyranosyl(1-4)]-β-D-gluco- pyranoside using spectroscopic and chemical methods.

Polyhydroxylated Steroidal Sapogenins from Tupistra wattii

Two novel polyhydroxylated steroidal sapogenins, wattigenin B ((25R)-spirost-1beta, 2beta, 3beta, 4beta, 5beta, 6beta, 7alpha-heptol, 1) and wattigenin C ((25S)-spirost-1beta, 2beta, 3beta, 4beta, 5beta, 7alpha-hexalrydroxyl-6-one, 2), together with two known sapogenins, kitigenin (3) and convallagenin B (4), were isolated froth the fresh rhizomes of Tupistra wattii Hook. f. The structures of the compounds were determined on the basis of spectroscopic analysis. The four sapogenins were evaluated for the cytotoxicities on the cancer cell line K562 and A2780a in vitro. Compounds 1 - 4 were obtained from the plant for the first time.

螺甾皂苷类化合物的体外抗人肝癌细胞增殖作用

目的通过体外实验初步探讨从茄科植物龙葵中提取的螺甾皂苷类化合物对人肝癌细胞株FHCC-98的细胞增殖抑制作用。方法采用MTT筛选由龙葵中提取分离的29种单体化合物,测定其在体外对人肝癌细胞株FHCC-98的生长抑制作用,以人正常肝细胞QSG7701为阴性对照。结果首先利用单浓度(100μmol/L)、单时间点(48h)对化合物进行初筛,其中有3个化合物符合要求,可以进行复筛,分别为solamar-gine;degalactotigonin;solasonine。复筛采用多浓度点(100,50,25,12.5,6.25μmol/L)、单时间点(48h)对化合物检测细胞毒性(IC50)。IC50值>100表示无细胞毒性。结论从龙葵中分离提取的螺甾皂苷类化合物solas-onine对人肝癌高侵袭细胞株的增殖具有一定抑制作用。

芦笋茎皮化学成分的研究

从芦笋茎皮中分得７个化合物，经理化常数测定和光谱分析，分别鉴定为：十六烷酸 （Ⅰ），二十四烷酸（Ⅱ），β－谷甾醇（Ⅲ），胡萝卜苷（Ⅳ），亚莫皂苷元－３－Ｏ－Ｌ－鼠李吡喃糖（１→４）β－Ｄ－ 葡萄吡喃糖苷（Ⅴ），ａｓｐａｒａｓａｐｏｎｉｎｌ（Ⅵ），ａｓｐａｒａｓａＰｏｎｉｎＩ（ Ⅵ）。 Ⅴ为首次从该属植物中分得的螺 旋皂苷。

瓜蒌薤白白酒汤螺甾皂苷类活性成分研究

目的 研究瓜蒌薤白白酒汤作用的物质基础。方法 在药理活性指导下利用各种化学和色谱手段对复方进行追踪分离并鉴定其化学结构。结果 从活性部位中分离得到 7个活性螺甾类化合物。结论 7个化合物均有抑制血小板聚集活性 ,其中化合物 5和

利用重组F26G酶实现呋甾皂苷向螺甾皂苷的体外生物转化

用BamHⅠ和XbaⅠ两种限制酶酶切质粒 pKG2 7,获得了编码F2 6G(F2 6G :furostanolgly coside 2 6 O β glucosidase)的cDNA ,然后将其重组到表达载体 pET 2 2b上而得到pET 2 2b CSF2 6G ,利用大肠杆菌E .coliBL2 1进行表达 ,用胞内可溶蛋白进行酶反应 ,通过TLC、HPLC分析证明重组菌表达出高活性的F2 6G酶 。

胡芦巴来源的甾体皂苷研究进展

中药胡芦巴是豆科一年生草本植物胡芦巴(Trigonella foenum-graecum L.)的干燥种子,富含甾体皂苷。本实验室对胡芦巴中甾体皂苷进行了系统研究,包括原生呋甾皂苷及其酶解产物的分离鉴定、利用液质联用技术对甾体皂苷类成分的快速表征与结构分析,以及利用超临界流体色谱技术对螺甾皂苷C-25R/S异构体的分析、制备分离等。本文对本实验室相关研究进行总结,以期有助于胡芦巴的开发与利用,也为今后中药的化学成分研究工作提供借鉴。

知母、麦冬和薯蓣中螺甾体皂苷的质谱裂解规律研究

目的:运用超高效液相色谱-串联质谱(UPLC-MS/MS)方法研究知母、麦冬和薯蓣中螺甾烷醇型甾体皂苷的[M+NH_4]^+离子质谱裂解行为。方法:采用电喷雾离子源,在阳离子模式下运用低、中、高不同碰撞能,研究5种螺甾烷醇型甾体皂苷质谱裂解规律。结果:总结了5种螺甾烷醇型甾体皂苷氨化离子的质谱裂解行为,其特征为螺甾烷醇型甾体皂苷首先失去17 Da,然后由外端至内端依次中性失去C-3上的各个糖基,生成特征性的[苷元+H]^+离子,最后[苷元+H]^+离子E环断裂脱去相应侧链和水分子。结论:阐明了螺甾烷醇型甾体皂苷质谱裂解行为,该研究将有助于知母、麦冬和薯蓣相关甾体皂苷类化合物的结构解析。

湖北山麦冬化学成分的研究

从湖北山麦冬(Liriope spicata Lout(Thunb).var.prolifera Y.T.Ma)块根的醇提物中分得四种甾体甙类化合物,根据化学性质和波谱(IR,~1HNMR,^(13)CNMR,EI-MS,FAB-MR)分析,确定甙Ⅰ为以β-谷甾醇为主、豆甾醇为次的混合甾醇的β-D-吡喃葡萄糖甙;甙Ⅱ为25(S)-鲁斯可皂甙元1-O-β-D-吡喃夫糖3-O-α-L-吡喃鼠李糖甙;甙Ⅲ为25(S)-鲁斯可皂甙元1-O-α-L-吡喃鼠李糖基(1→2)-β-D-吡喃木糖甙;甙Ⅳ为25(S)-鲁斯可皂甙元1-O-[α-L-吡喃鼠李糖基(1→2)](β-D-吡喃木糖基(1→3)]-β-D-吡喃夫糖甙,其中甙Ⅲ和甙Ⅳ为新的甾体皂甙。

小桃儿七螺甾烷皂苷及其抗肿瘤细胞活性

利用层析法从小桃儿七中分离得到单体螺甾烷皂苷,利用核磁共振波谱技术鉴定其结构,采用MTT法测试其体外乳腺癌MCF-7细胞株、人宫颈癌Hela细胞株和人肝癌Hep G2细胞株的细胞毒活性,检测其对正常929细胞株的细胞毒活性。结果表明,该单体对人宫颈癌Hela细胞株具有抑制作用(IC50=71.23μmol/L),对正常929细胞株无明显抑制作用。

洋河大曲中螺甾醇健康功能因子研究

白酒是我国最重要的传统发酵食品之一,在世界范围内享有很高的声誉。曲药被称为酒之骨,决定了白酒的风格和品质,对白酒酿造起着举足轻重的作用。目前,主要采用顶空-固相微萃取与气质联用的方法研究大曲中低沸点香味物质,对大曲中高沸点难挥发成分研究鲜有报道。本研究以洋河酒厂提供的大曲为材料,利用95%vol乙醇进行提取,结合正相硅胶、反相硅胶、Sephadex LH-20等多种色谱技术,从大曲中分离得到6个螺甾醇类化合物,应用核磁共振、质谱等波谱技术分别将其鉴定为sarsasapogenin(1)、7α-hydroxysarsasapogenin(2)、yamogenin(3)、diosgenin(4)、neotigogenin(5)和tigogenin(6)。本研究首次从洋河大曲中发现了具有广泛生理活性的螺甾醇类小分子,为揭示中国白酒的健康功能因子奠定了基础。