New C-glycosylflavones from Mollugo distica

Four C-glycosylflavones isolated from Mollugo distica were identified as 8-C-β-d-glucopyranosyl-genkwanin, 8-C-α-l-arabinopyranosylgenkwanin and their 2″-rhamnosides.     

Two new neoflavonoids and C-glycosylflavones from Passiflora serratodigitata

The aerial parts of Passiflora serratodigitata yielded 5,7-dihydroxy-4-phenylcoumarin, its 7-β-glucoside and the known C-glycosylflavones 2″-xylosylvitexin, 2″-xylosylisovitexin, vitexin, isovitexin, a vicenin, and orientin. The known flavone chrysin was also isolated. This is the first report of neoflavonoids in the family Passifloraceae.     

New C-glycosylflavones from Cerastium arvense

Three C-glycosylflavones isolated from Cerastium arvense have been identified as 6-C-xylosyl-apigenin (cerarvensin), its 7-O-glucoside and isovitexin 7,2″-di-O-glucoside.     

C-Glycosylflavones from Avena sativa

Avena sativa leaves, stems and inflorescences contain a range of new C-glycosylflavone 2″-O-glycosides, including vitexin and isoswertisin 2″-rhamnosides, isovitexin and isoorientin 2″-arabinosides. The structure of ‘vitexin 4′-rhamnoside’ from Crataegus oxyacantha is revised in vitexin 2″-rhamnoside.     

C-glycosylanthocyanidins synthesized from C-glycosylflavones

Nine C-glycosyldeoxyanthocyanidins, 6-C-β-glucopyranosyl-7-O-methylapigeninidin, 6-C-β-glucopyranosyl-7-O-methylluteolinidin, 6-C-β-(2″-O-β-glucopyranosylglucopyranosyl)-7-O-methylapigeninidin, 6-C-β-(2″-O-β-glucopyranosylglucopyranosyl)-7,4′-di-O-methylapigeninidin, 8-C-β-glucopyranosylapigeninidin, 8-C-β-(2″-O-α-rhamnopyranosylglucopyranosyl)apigeninidin, 8-C-β-(2″-O-α-(4″′-O-acetylrhamnopyranosyl)glucopyranosyl)apigeninidin, 6,8-di-C-β-glucopyranosylapigeninidin (8), 6,8-di-C-β-glucopyranosyl-4′-O-methylluteolinidin (9), have been synthesized from their respective C-glycosylflavones (yields between 14% and 32%) by the Clemmensen reduction reaction using zinc-amalgam. The various precursors (C-glycosylflavones) of the C-glycosylanthocyanidins were isolated from either flowers of Iris sibirica L., leaves of Hawthorn ‘Crataegi Folium Cum Flore’, or lemons and oranges. This is the first time C-glycosylanthocyanidins have been synthesized. The structures of all flavonoids including the flavone rotamers were elucidated by 2D NMR techniques and high-resolution electrospray MS. The distribution of the various structural forms of 8 and 9 are different at pH 1.1, 4.5, and 7.0, however, the two pigments undergoes similar structural transformations at the various pH values. Pigments 8 and 9 with C-C linkages between the sugar moieties and the aglycone, were found to be far more stable towards acid hydrolysis than pelargonidin 3-O-glucoside, which has the typical anthocyanidin C-O linkage between the sugar and aglycone. This stability may extend the present use of anthocyanins as nutraceuticals, pharmaceuticals or colorants.     

Flavonoid diversification in different leaf compartments of Primula auricula (Primulaceae)

Populations of Primula auricula L. subsp. auricula from Austrian Alps were studied for flavonoid composition of both farinose exudates and tissue of leaves. The leaf exudate yielded Primula-type flavones, such as unsubstituted flavone and its derivatives, while tissue flavonoids largely consisted of flavonol 3-O-glycosides, based upon kaempferol (3, 4) and isorhamnetin (5–7). Kaempferol 3-O-(2″-O-β-xylopyranosyl-[6″-O-β-xylopyranosyl]-β-glucopyranoside) (3) and isorhamnetin 3-O-(2″-O-β-xylopyranosyl-[6″-O-β-xylopyranosyl]-β-glucopyranoside) (6) are newly reported as natural compounds. Remarkably, two Primula type flavones were also detected in tissues, namely 3′-hydroxyflavone 3′-O-β-glucoside (1) and 3′,4′-dihydroxyflavone 4′-O-β-glucoside (2), of which (1) is reported here for the first time as natural product. All structures were unambiguously identified by NMR and MS data. Earlier reports on the occurrence of 7,2′-dihydroxyflavone 7-O-glucoside (macrophylloside) in this species could not be confirmed. This structure was now shown to correspond to 3′,4′-dihydroxyflavone 4′-O-glucoside (2) by comparison of NMR data. Observed exudate variations might be specific for geographically separated populations. The structural diversification between tissue and exudate flavonoids is assumed to be indicative for different ecological roles in planta.     

Xanthones from Tovomita pyrifolium

The wood of Tovomita pyrifolium (Guttiferae) contains the novel tovopyrifolins A [1,6-dihydroxy-7-methoxy-5-prenyl-6′,6′-dimethylpyrano (2′,3′:3,2)xanthone], B (1,5-dihydroxy-3,4-dimethoxyxanthone) and C (1,3,5-trihydroxy-2-methoxyxanthone) and also the known tovophyllins A and B [structure revised to 1,6-dihydroxy-5-prenyl-6′, 6′-dimethylpyrano(2′,3′:3,2)-6″,6″-dimethylpyrano(2″,3″:7,8)xanthone].     

Quercetin 3-(6″-caffeoylgalactoside) from Hydrocotyle sibthorpioides

In addition to quercetin, quercetin 3-galactoside and isorhamnetin, a new caffeoylgalactoside has been isolated from Hydrocotyle sibthorpioides and identified by chemical and spectral data as quercetin 3-O-β-d-(6″-caffeoylgalactoside).     

Nouvelles C-glycosylflavones extraites de Spergularia rubra

Three 6,8-di-C-glucosylflavones: 6,8-di-C-β-d-glucopyranosylapigenin, luteolin and chrysoeriol were isolated from the whole plant of Spergularia rubra. Two new compounds, 7,2″-di-O-β-d-glucopyranosyl-6-C-α-l-arabinopyranosylapigenin and 6-C-α-l-arabinopyranosylapigenin (isomollupentin), were also characterized. Structural assignments were based on ¹H NMR and MS spectra and on comparison with synthetic samples. MS fragmentation patterns of the new di-O-glucosyl compound PM derivative and of its acid hydrolysis product are given.     

Isomollupentin-O-glucosides from Cerastium arvense

Eight C-glycosylflavone O-glycosides including three new compounds: isomollupentin 7-O-glucoside, isomollupentin 4′-O-glucoside and isomollupentin 2″-O-glucoside have been isolated from the leaves and flowers of Cerastium arvense. The 27 C-glycosylflavones identified in this plant are tabulated.     

Flavone C-glycosides from Coronilla varia

One new and 5 known flavone C-glycosides were isolated from leaves and stems of Coronilla varia. The new compound was shown to be isoorientin 2″-O-rhamnoside. The known compounds were isovitexin, isoorientin, isovitexin 4′-O-glucoside, isoorientin 4′-O-glucoside, and isoorientin 7-O-glucoside.     

Dihydrochalcone glucosides and antioxidant activity from the roots of Anneslea fragrans var. lanceolata

Bioassay-guided fractionation of the roots of Anneslea fragrans var. lanceolata led to the isolation of four dihydrochalcone glucosides, davidigenin-2′-O-(6″-O-4″′-hydroxybenzoyl)-β-glucoside (1), davidigenin-2′-O-(2″-O-4″′-hydroxybenzoyl)-β-glucoside (2), davidigenin-2′-O-(3″-O-4″′-hydroxybenzoyl)-β-glucoside (3), and davidigenin-2′-O-(6″-O-syringoyl)-β-glucoside (4), and 13 known compounds. The structures were identified by means of spectroscopic analysis. Davidigenin-2′-O-(6″-O-syringoyl)-β-glucoside (4), 1-O-3,4-dimethoxy-5-hydroxyphenyl-6-O-(3,5-di-O-methylgalloyl)-β-glucopyranoside (5), lyoniresinol (10), and syringic acid (13) showed ABTS [2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid)] cation radical scavenging activity, with SC₅₀ values of 52.6 ± 5.5, 26.0 ± 0.7, 6.0 ± 0.2, and 27.5 ± 0.6 μg/mL in 20 min, respectively. Lyoniresinol (10), isofraxidin (12), and syringic acid (13) also showed DPPH [1,1-diphenyl-2-picrylhydrazyl] radical scavenging activity, with SC₅₀ values of 8.4 ± 1.8, 51.6 ± 2.2, and 4.3 ± 0.7 μg/mL in 30 min, respectively.     

Acetylated allose-containing flavonoid glucosides from Stachys anisochila

In continuation of our chemosystematic study of Stachys (Labiatae) we have isolated the previously reported isoscutellarein 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-β-D-glucopyranoside] (1) and 3′-hydroxy-4′-O-methylisoscutellarein 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-β-D-glucopyranoside] (4) and four new allose-containing flavonoid glycosides from S. anisochila. The new glycosides are hypolaetin 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-β-D-glucopyranside] (6) as well as the three corresponding diacetyl analogues of 1, 4 and 6, isoscutellarein 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-6″-O-acetyl-β-D-glucopyranoside], 3′-hydroxy-4′-O-methylisoscutellarein 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-6″-O-acetyl-β-D-glucopyranoside] and hypolaetin 7-O-[6″'-O-acetyl-β-D-allopyranosyl-(1 → 2)-6″-O-acetyl-β-D-glucopyranoside]. Extensive two-dimensional NMR studies (proton-carbon correlations, COSY experiments) allowed assignment of all ¹H NMR sugar signals and a correction of the ¹³C NMR signal assignments for C-2 and C-3 of the allose.     

Flavonol glycoside gallates from Tellima grandiflora

Quercetin 3-O-(6″-O-galloyl)-β-d-glucoside has been identified as a constituent of Tellima grandiflora (Saxifragaceae). In all, twelve gallates were encountered: two isomeric gallates of quercetin 3-O-glucoside and two of quercetin 3-O-galactoside, a similar set involving kaempferol, and a similar set involving myricetin.     

Biosynthesis of a water solubility-enhanced succinyl glucoside derivative of luteolin and its neuroprotective effect

The natural flavonoids luteolin and luteoloside have anti-bacterial, anti-inflammatory, anti-oxidant, anti-tumour, hypolipidemic, cholesterol lowering and neuroprotective effects, but their poor water solubility limits their application in industrial production and the pharmaceutical industry. In this study, luteolin-7-O-β-(6″-O-succinyl)-d -glucoside, a new compound that was prepared by succinyl glycosylation of luteolin by the organic solvent tolerant bacterium Bacillus amyloliquefaciens FJ18 in an 8.0% DMSO (v/v) system, was obtained and identified. Its greater water solubility (2293 times that of luteolin and 12 232 times that of luteoloside) provides the solution to the application problems of luteolin and luteoloside. The conversion rate of luteolin (1.0 g l⁻¹) was almost 100% at 24 h, while the yield of luteolin-7-O-β-(6″-O-succinyl)-d -glucoside reached 76.2%. In experiments involving the oxygen glucose deprivation/reoxygenation injury model of mouse hippocampal neuron cells, the cell viability was significantly improved with luteolin-7-O-β-(6″-O-succinyl)-d -glucoside dosing, and the expressions of the anti-oxidant enzyme HO-1 in the nucleus increased, providing a neuroprotective effect for ischemic cerebral cells. The availability of biosynthetic luteolin-7-O-β-(6″-O-succinyl)-d -glucoside, which is expected to replace luteolin and luteoloside, would effectively expand the clinical application value of luteolin derivatives.     

C-Glycosylflavones from Gnetum buchholzianum and Gnetum africanum

C-Glycosylflavones, including two new compounds 2″-xylosylisoswertisin and 2″-glucosylisoswertisin, were isolated from the leaves of Gnetum buchholzianum and G. africanum. The occurrence of apigenin 7-neohesperidoside distinguishes the latter from the first species.     

Flavonoid glycosides from needles of Pinus massoniana

Seven flavonoids have been isolated from Pinus massoniana needles and identified as taxifolin and its 3′-O-β-D-glucopyranoside, (+)-catechin, naringenin-7-O-β-D-glucopyranoside and three new flavonoid glycosides, 6-C-methylaromadendrin 7-O-β-D-glucopyranoside, taxifolin 3′-O-β-D-(6″-O-phenylacetyl)-glucopyranoside and eriodictyol 3′-O-β-D-glucopyranoside.     

Anthraquinone,anthrone and phenylpyrone components of Aloe nyeriensis var. kedongensis leaf exudate

The leaf exudate of Aloe nyeriensis var. kedongensis yielded six compounds which were identified on the basis of spectral data and inter-conversions as two groups of three allied compounds. These were (a) 4-methoxy-6(2′,4′-dihydroxy-6′- methylphenyl)-pyran-2-one, its 2′-O-β-D-glucopyranoside (aloenin) and the 2″-O-p-coumaroyl ester of aloenin, (b) the anthracene derivatives l,2,8-trihydroxy- 6-methylanthraquinone (nataloe-emodin), its 2-O-β-D-glucopyranosyl ester and the corresponding 10-C -β-D-glucopyranoside nataloin.     

Fragmentation pattern of permethyl 6-C-glycosylflavones in electron impact mass spectrometry

A mass spectral fragmentation pattern of permethyl 6-C-glycosylflavones is proposed from the MS data of permethyl derivatives mono-O-deuteriomethylated in the 2″-, 3″-, 4″- or 6″-positions. The synthesis of these compounds via O″-glycosyl-6-C-glucosylflavones is described.     

An acylated flavone apigenin 7-O-β-D-(4″-cis-p-coumaroyl)glucoside from Echinops echinatus

Besides apigenin 7-O-glucoside, a new acylated flavone has been identified in Echinops echinatus as apigenin 7-O-β-D-(4″-cis-p-coumaroyl)glucoside from spectral and chemical analysis.