Cyanohydrin glycosides of Passiflora: distribution pattern, a saturated cyclopentane derivative from P. guatemalensis, and formation of pseudocyanogenic α-hydroxyamides as isolation artefacts

• Published in: Phytochemistry (Oxford) 2002-03, Vol.59 (5), p.501-511
• Main Authors: Jaroszewski, Jerzy W, Olafsdottir, Elin S, Wellendorph, Petrine, Christensen, Jette, Franzyk, Henrik, Somanadhan, Brinda, Budnik, Bogdan A, Bolt Jørgensen, Lise, Clausen, Vicki
• Format: Article
• Language: English
• Subjects: Amides - metabolism; Biological and medical sciences; Chemotaxonomy; Chromatography, High Pressure Liquid; Cyanogenesis; Dihydrogynocardin; Fundamental and applied biological sciences. Psychology; Glycosides - chemistry; Glycosides - metabolism; Helix pomatia; Magnetic Resonance Spectroscopy; Metabolism; Metabolism. Physicochemical requirements; Nitriles - chemistry; Nitriles - metabolism; Passiflora; Passiflora - metabolism; Passifloraceae; Passiguatemalin; Plant cytology, morphology, systematics, chorology and evolution; Plant physiology and development; Spermatophyta; Systematics (diagnosis, chromosome numbers); α-Hydroxyamides
• ISSN: 0031-9422; 1873-3700
• DOI: 10.1016/S0031-9422(01)00485-X

Nineteen species of Passiflora (Passifloraceae) were examined for the presence of cyanogenic glycosides. Passibiflorin, a bisglycoside containing the 6-deoxy-β- d-gulopyranosyl residue, was isolated from P. apetala, P. biflora, P. cuneata, P. indecora, P. murucuja and P. perfoliata. In some cases this glycoside co-occurs with simple β- d-glucopyranosides: tetraphyllin A, deidaclin, tetraphyllin B, volkenin, epivolkenin and taraktophyllin. P. citrina contains passicapsin, a rare glycoside with the 2,6-dideoxy-β- d- xylo-hexopyranosyl moiety, while P. herbertiana contains tetraphyllin A, deidaclin, epivolkenin and taraktophyllin, P. discophora tetraphyllin B and volkenin, and P. × violacea tetraphyllin B sulfate. The remaining species were noncyanogenic. The glycosides were identified by 1H and 13C NMR spectroscopy following isolation by reversed-phase preparative HPLC. From P. guatemalensis, a new glucoside named passiguatemalin was isolated and identified as a 1-(β- d-glucopyranosyloxy)-2,3-dihydroxycyclopentane-1-carbonitrile. An isomeric glycoside was prepared by catalytic hydrogenation of gynocardin. α-Hydroxyamides corresponding to the cyanogenic glycosides were isolated from several Passiflora species. These α-hydroxyamides, presumably formed during processing of the plant material, behave as cyanogenic compounds when treated with commercial Helix pomatia crude enzyme preparation. Thus, the enzyme preparation appears to contain an amide dehydratase, which converts α-hydroxyamides to cyanohydrins that liberate cyanide; this finding is of interest in connection with analysis of plant tissues and extracts using Helix pomatia enzymes. Distribution of various types of cyclopentanoid cyanohydrin glycosides in Passiflora is shown to be highly structured at the subgenus level; glycoside 1 was isolated; glucuronidase/sulfatase from Helix pomatia contains an amide dehydratase activity, which renders α-hydroxyamides such as 2 cyanogenic.