Unprecedented C_(19)-diterpenoid alkaloid glycosides from an aqueous extract of “fu zi”: Neoline 14-O-L-arabinosides with four isomeric L-anabinosyls

Four structurally unprecedented aconitane-type C_(19)-diterpenoid alkaloid glycosides with isomeric arabinosyls, named aconicarmichosides A–D(1–4), were isolated from an aqueous extract of "fu zi", the lateral roots of Aconitum carmichaelii. Their structures were determined as neoline 14-O-a-and 14-O-b-L-arabinopyranosides(1 and 2) and 14-O-a-and 14-O-b-L-arabinofuranosides(3 and 4), by spectroscopic and chemical methods including 2D NMR experiments and acid hydrolysis. Compounds 1–4 represent the first examples of glycosidic diterpenoid alkaloids.     

Separation of saponins and determination of quinovic acid 3-O-α-L-rhamnopyranoside fromNauclea diderrichii (de Wild) Merr. Bark by high performance liquid chromatography

Summary A reversed-phase HPLC determination of 11 saponins and an alkaloid glycoside inNauclea diderrichii bark is described. Quantitative analysis of quinovic acid 3-0-α-L-rhamnopyranoside which is one of the main saponins was determined, using Chrysanthelline A as internal standard. The complete separation was achieved in 47 minutes. The method of quantification was validated.     

一种新的测定一维同核全相关的NMR技术

提出一种新的基于MDY混合脉冲的可测定一维同核全相关的核磁共振技术.称为一维自旋回波MDY相干转移(lD-SEMDY)实验.结果表明.它具有下列突出优点:一是不用Z-滤波技术就可以得到纯吸收型的一维全相关谱(lD-TOCSY).与同类技术相比,操作简便.可节省测定时间.应用范围较广;二是所测定亚谱中的信号归属通过改变混合时间和延迟时间可以得到确定;三是相干转移非常有效.远程磁化转移信号的灵敏度比较高,对弱偶合的自旋体系也可进行测定.以甙类化合物为例讨论了它在谱峰高度重叠的有机结构测定中的应用.     

A New Flavanone and a New Flavanone Glycoside from ScuteUaria baicalensis

A new flavanone （2S）-5, 7, 2＇, 5＇-tetrahydroxy-flavanone 1 together with a new flavanone glycoside （2S）-5, 7, 2＇, 5＇-tetrahydroxy-flavanone 7-O-13-D-glucopyranoside 2, were isolated from the dry roots of Scutellaria baicalensis. Their structures were elucidated on the basis of spectroscopic data.     

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.     

Isatindigodiphindoside,an alkaloid glycoside with a new diphenylpropylindole skeleton from the root of Isatis indigotica

A novel indole alkaloid glycoside with an unprecedented 2-(diphenylpropyl)-indole skeleton, isatindigodiphindoside (1), was isolated from an aqueous extract of the roots of Isatis indigotica. The structure was determined by extensive spectroscopic studies, especially by 2D NMR data analysis combined with enzymatic hydrolysis and ECD calculations. Plausible biosynthetic pathways of compound 1 are also discussed.     

Angustifolinoid A,a macrocyclic flavonoid glycoside from Elaeagnus angustifolia flowers

A novel macrocyclic flavonoid glycoside, angustifolinoid A (1), featuring an unprecedented 13-membered heterocyclic ring moiety, along with a known flavonoid glycoside, tiliroside (2), were isolated from Elaeagnus angustifolia flowers. Their structures were determined by extensive spectroscopic analysis and electronic circular dichroism (ECD) calculation. Biosynthesis analysis indicated that compound 1 might be derived from compound 2 via a key enzymatic intramolecular oxidative coupling. Compounds 1 and 2 showed inhibitory activities against cyclooxygenases, COX-1 and COX-2.     

Efficient total syntheses of natural pterin glycosides: limipterin and tepidopterin

The key, versatile precursors N²-(N,N-dimethylaminomethylene)-1′-O-(4-methoxybenzyl)-3-[2-(4-nitrophenyl)ethyl]biopterin (29a) and its ciliapterin analog (29b) were prepared, respectively, from d-xylose (in 14 steps) and l-xylose (in 11 steps). Treatment of 29a and 29b with 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-d-glucopyranosyl bromide in the presence of silver triflate and tetramethylurea, followed by removal of the protecting groups, led to the first selective syntheses of limipterin (3) and tepidopterin (5), respectively.     

Mechanistic studies on the formation of glycosidase-substrate and glycosidase-inhibitor covalent intermediates

Glycoside hydrolases catalyze the breaking of the glycosidic bond. This type of bond fashioned between two monosaccharides is very stable, and the polymers created are involved in multiple cellular processes, being crucial to life. In this article, computational methods were used to study the first step of the mechanism of reaction of retaining glycoside hydrolases in atomic detail. The systems modeled included a simplified reaction center and a small substrate/inhibitor. Using DFT calculations we were able to corroborate and provide molecular-level detail to the dissociative mechanism proposed in the literature. The role of the hydrogen bridge between the nucleophile and the C(2)--OH group of the ring was also investigated. Therefore, we concluded that this bridge is responsible for lowering the activation barrier by 5.1 kcal mol(-1) with functional BB1K/6-311+G(2d,2p), and the absence of the bridge explains, at least in part, the inhibitory effect of fluoro-substituted glycosides in the -2 position. The hydrogen bridge could also be involved in favoring the ring distortion verified in the transition state, and the dissociative character of the reaction mechanism. Using the NBO method, point atomic charges were calculated. In the transition state, the positive charge generated in the sugar ring is distributed nearly equally between the anomeric carbon and the ring oxygen, through a partial double bond involving the two atoms.