One‐Pot Synthesis of Hydrophobically Modified Iminosugar C‐Alkynylglycosides: Facile Synthesis of Polyhydroxy Tetrahydroindolizines

A mild and efficient one‐pot method has been developed for the stereoselective synthesis of structurally diverse novel iminosugar C‐alkynylglycosides. The generality of this methodology has been demonstrated with a wide variety of amines and copper acetylides. This one‐pot method has been exploited in the synthesis of new class of DNA cross‐linking agents, polyhydroxy 1‐vinyl‐tetrahydroindolizine derivatives.     

Complete NMR spectral assignments of two lactucin-type sesquiterpene lactone glycosides from Picris conyzoides

Complete (1)H and (13)C NMR signal assignments of two lactucin-type sesquiterpene lactone glycosides, derivatives of 11β,13-dihydrolactucin, isolated from roots of Picris conyzoides, were achieved by one- and two-dimensional NMR experiments, allowing the correction of previously published data for cichorioside B and the structure elucidation of its new ester with 3-hydroxy-2-methylpropanoic acid. In addition, seven known sesquiterpene lactones and three phenolic compounds were isolated from the plant material.     

Synthesis and biological evaluation of prodrugs based on the natural antibiotic duocarmycin for use in ADEPT and PMT

Chemotherapy of malign tumors is usually associated with serious side effects as common anticancer drugs lack selectivity. An approach to deal with this problem is the antibody-directed enzyme prodrug therapy (ADEPT) and the prodrug monotherapy (PMT). Herein, the synthesis and biological evaluation of new glycosidic prodrugs suitable for both concepts are described. All prodrugs but one are stable in human serum and show QIC(50) values (IC(50) of prodrug/IC(50) of prodrug in the presence of the appropriate glycohydrolase) of up to 6500. This is the best value found so far for compounds interacting with DNA.     

New Triterpenoid and Ergostane Glycosides from the Leaves of Hydrocotyle umbellata L.

Two new triterpenoid glycosides, together with two new ergostane glycosides, umbellatosides A–D ( 1 – 4 , resp.), have been isolated from the leaves of Hydrocotyle umbellata L. Their structures were established by 2D‐NMR spectroscopic techniques (¹H,¹H‐COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry as 3β,22β‐dihydroxy‐3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]olean‐12‐en‐28‐oic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 1 ), 3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]oleanolic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 2 ), (3β,11α,26)‐ergosta‐5,24(28)‐diene‐3,11,26‐triol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 3 ), and (3β,11α,21,26)‐ergosta‐5,24(28)‐diene‐3,11,21,26‐tetrol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 4 ).     

FTIR光谱快速鉴别刺梨黄酮的研究

采用傅里叶变换红外光谱（FTIR）分析了新鲜野生刺梨果肉、烘干刺梨果肉以及室温存放数日后刺梨果肉的红外光谱特性。为对比新鲜果肉与烘干果肉样品中刺梨黄酮的红外光谱特性,以新鲜野生刺梨果实为研究对象,分别采用了超声辅助溶剂萃取法和超声结合酶辅助半仿生法提取刺梨黄酮。并使用无水乙醇作为超声辅助溶剂萃取法的萃取剂萃取刺梨黄酮,以及使用胃蛋白酶,胰酶和胆汁等模仿胃肠消化的环境,在模拟半仿生条件下提取刺梨黄酮。在两种提取方法中,新鲜果肉和烘干果肉分别反应了0,0.5,1,1.5,2和2.5 h。分别测定了新鲜果肉刺梨黄酮和烘干果肉刺梨黄酮的红外光谱数据。然后,通过分析刺梨黄酮的红外光谱特性,比较了两种方法所提取刺梨黄酮的最佳特征波长组合,得知在相同的反应条件下,反应时间为1.5 h时,超声辅助溶剂萃取法中新鲜果肉与烘干果肉提取物红外光谱对应的透射率强度分别为83.5%和84%;超声结合酶辅助半仿生法中新鲜果肉与烘干果肉提取物红外光谱对应的透射率强度分别为32%和38%。因此,结合郎伯-比尔定律可知,反应时间相同时,对于刺梨黄酮的提取,超声结合酶辅助半仿生法优于超声辅助溶剂萃取法。除此之外,我们发现随着反应时间延长,两种提取方法所获提取物的红外光谱吸收峰强度均呈上升趋势,但是反应2 h后该提取物的红外光谱吸收峰强度趋于平稳。结果表明,刺梨黄酮在3 419 cm-1（羟基O-H伸缩振动）、1 615 cm-1（羰基C═O键伸缩振动）和1 053 cm-1（烷基）处的红外吸收峰对刺梨的新鲜程度具有较好的识别效果;通过比较分析,新鲜果肉与室温存放数日后果肉中的刺梨黄酮物质的红外光谱吸收峰分别与槲皮素和山奈酚吸收峰波数一致;在相同实验条件下,两种提取方法中烘干果肉刺梨黄酮提取物浓度均高于新鲜刺梨果肉。该研究可为刺梨功能化药品和食品的制作及鉴定提供参考。     

Synthesis and antitumor activity of a group of diosgenyl glycosides

Using orthogonal protection-deprotection glycosylation strategy, a series of diosgenyl glycosides with same of monosaccharides component but different in sequence were synthesized. The antitumor activity in vitro of synthesized diosgenyl glycosides was evaluated by standard MTT assay. It was observed that diosgenyl glycosides with a rhamnopyranosyl at C2′ of glucopyranosyl residue show potent antitumor activity in vitro.     

黄酮甙类化合物中的酰基取代及其取代位置的确定

研究了黄酮甙类化合物的酰基取代现象，借助２ Ｄ ＮＭＲ技术，举例研究了一黄酮醇三乙酰基三糖甙的结构，着重研究糖上酰基的取代位置，并归纳总结了黄酮甙类化合物中各种常见的酰基的＾１３ ＣＮＭＲ谱及其取代所产生的位移现象。     

Two New Flavonol Glycosides from Bridelia tomentosa

Bridelia tomentosa Bl., a small shrub in the Euphorbiaceae family, is widely distributed in Taiwan, Guangdong, Guangxi and Yunnan Provinces of south China. As a traditional medicine, it is used for curing neurasthenic, turbulence of emmenia, bite of dog, …     

Characterisation of proanthocyanidin aglycones and glycosides from rose hips by high-performance liquid chromatography-mass spectrometry, and their rapid quantification together with vitamin C

Fifteen individual proanthocyanidin aglycones and 19 glycosides, together with a complex mixture of chromatographically non-separated tetra- to octameric proanthocyanidin glycosides were detected--the non-separated glycosides being novel natural products--and characterised from dog rose hips using high-performance liquid chromatography-electrospray ionisation mass spectrometry (HPLC-ESI-MS). Along with these phenolics, a 50% aqueous ethanol extract of rose hips was found to contain high levels of Vitamin C. A simple and rapid HPLC method assisted by diode array detection for the estimation of the total concentration of proanthocyanidin aglycones and glycosides, as well as Vitamin C, in rose hip extracts was developed.