Novel Glycosidic Constituents from Saffron

Abstract

The methanolic extract of saffron was prefractionated with the aid of multilayer coil countercurrent chromatography (MLCCC). After subsequent purification of certain fractions by high-performance liquid chromatography, the following glycoconjugates were isolated and identified on the basis of their spectral (UV, MS, NMR) data: the β-d-glucosides of (4R)-4-hydroxy-3,5,5-trimethylcyclohex-2-enone (5), (4S)-4-hydroxy-3,5,5-trimethylcyclohex-2-enone (6), and (4S)-4-(hydroxymethyl)-3,5,5-trimethylcyclohex-2-enone (7), as well as the β-d-gentiobiosyl ester of 2-methyl-6-oxohepta-2,4-dienoic acid (4). In addition to these new natural products, known saffron constituents, i.e., the di-β-d-gentiobiosyl and β-d-gentiobiosyl-β-d-glucopyranosyl esters of crocetin, have also been isolated and separated using MLCCC. Keywords: (4R)-4-Hydroxy-3,5,5-trimethylcyclohex-2-enone 4-O-β-d-glucopyranoside; (4S)-4-hydroxy-3,5,5-trimethylcyclohex-2-enone 4-O-β-d-glucopyranoside; (4S)-4-(hydroxymethyl)-3,5,5-trimethylcyclohex-2-enone 4-O-β-d-glucopyranoside; β-d-gentiobiosyl ester of 2-methyl-6-oxohepta-2,4-dienoic acid; crocetin derivatives; carotenoid degradation products; multilayer coil countercurrent chromatography; saffron; Crocus sativus; Iridaceae

Metabolomic fingerprinting of saffron by LC/MS: novel authenticity markers

“…All these data (see Table 3 and Fig. 5a), according to previously published data [40], confirmed the structure of kaempferol 3-Osophoroside as the compound eluting at 7.7 min, the main saffron flavonoid (about 55 % of total flavonols content), whose presence was reported previously in C. sativus in several works [39,[41][42][43][44][45]. In addition, Carmona et al [46] stated that saffron samples from different Table 3 MS and MS/MS data (in positive and negative ESI modes) for several compounds tentatively identified in Table 2 This sugar substitution takes place at the hydroxyls in the following order of preference (from more to less) at the 3-, 7-and 4′-positions of the flavonoid nucleus [47].…”

Constituents of the Pollen of Crocus sativus L. and Their Tyrosinase Inhibitory Activity.

“…From the above results, structure 3 was assigned for crocusatin-C. Though this compound was synthesized by Surmatis et al,16) and also obtained as a hydrolysis product of (4S)-4-(hydroxymethyl)-3,5,5-trimethylcyclohex-2-enone-b-D-glucopyranoside, 17) this is the first example from the natural source.…”

Production Practices and Quality Assessment of Food Crops Volume 1

“…Methanol-water (Koyama et al, 1988;Tarantilis et al, 1995;Orfanou and Tsimidou, 1996;Straubinger et al, 1997;Lozano et al, 1999;Soeda et al, 2001), ethanolwater (Buchecker and Eugster, 1973;Speranza et al, 1984;Gómez et al, 1987b;Himeno and Sano, 1987;Visvanath et al, 1990;Oberdieck et al, 1991;Sujata et al, 1992;Loskutov et al, 2000) diethyl ether (Zarghami and Heinz, 1971;Pfander and Schurtenberger, 1982;Tarantilis and Polissiou, 1997;Zareena et al, 2001) petroleum ether (Tarantilis et al, 1994b) or aqueous extracts of saffron (Basker and Negbi, 1985;Alonso et al, 1990;Iborra et al, 1992a;Iborra et al, 1992b;Orfanou and Tsimidou, 1996;Tsimidou and Billiaderis, 1997;Selim et al, 2000) have been used. Methanol-water (Koyama et al, 1988;Tarantilis et al, 1995;Orfanou and Tsimidou, 1996;Straubinger et al, 1997;Lozano et al, 1999;Soeda et al, 2001), ethanolwater (Buchecker and Eugster, 1973;Speranza et al, 1984;Gómez et al, 1987b;Himeno and Sano, 1987;Visvanath et al, 1990;Oberdieck et al, 1991;…”