Steroidal glycosides from the underground parts of Helleborus caucasicus.
Four polyhydroxylated and polyunsaturated furostanol glycosides (1-4), named caucasicosides A (1), B (2), C (3) and D (4), were isolated from the MeOH extract of the underground parts of Helleborus caucasicus, along with four spirostanol derivatives, a furostanol glycoside, a furospirostanol glycoside, 20-hydroxyecdysone and the bufadienolides hellebrigenin and deglucohellebrin. The structures of 1-4 were elucidated as furosta-5,20(22),25(27)-triene-1beta,3beta,11alpha,26-tetrol 26-O-beta-D-glucopyranoside (1), 26-O-beta-D-glucopyranosylfurosta-5,20(22),25(27)-triene-1beta,3beta,11alpha,26-tetrol 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (2), 26-O-beta-d-glucopyranosyl-22alpha-methoxyfurosta-5,25(27)-diene-1beta,3beta,11alpha,26-tetrol 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (3), 26-O-beta-D-glucopyranosylfurosta-5,20(22),25(27)-triene-1beta,3beta,26-triol 3-O-beta-D-xylopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-4-O-sulfo-alpha-L-arabinopyranoside (4). Structure elucidation was accomplished through the extensive use of 1D- and 2D NMR experiments including 1H-1H (COSY, 1D-TOCSY) and 1H-13C (HSQC, HMBC) spectroscopy along with ESI-MS and HR-ESI-MS. The aglycones of 1-4 have never been reported before.
Bassarello
Carla
C
Dipartimento di Scienze Farmaceutiche, Università degli Studi di Salerno, Via Ponte Don Melillo, 84084 Fisciano SA, Italy.
Muzashvili
Tamara
T
Skhirtladze
Alexandre
A
Kemertelidze
Ether
E
Pizza
Cosimo
C
Piacente
Sonia
S
D006027:Glycosides / Q000737:chemistry* / Q000302:isolation & purification; D039322:Helleborus / Q000737:chemistry*; D006868:Hydrolysis; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008968:Molecular Conformation; D018517:Plant Roots / Q000737:chemistry*; D012015:Reference Standards; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D013237:Stereoisomerism; D013256:Steroids / Q000737:chemistry* / Q000302:isolation & purification; D013431:Sulfates / Q000032:analysis
D006027:Glycosides; D013256:Steroids; D013431:Sulfates