Cyanogenic allosides and glucosides from Passiflora edulis and Carica papaya

• Published in: Phytochemistry (Oxford) 2002-08, Vol.60 (8), p.873-882
• Main Authors: Seigler, David S., Pauli, Guido F., Nahrstedt, Adolf, Leen, Rosemary
• Format: Article
• Language: English
• Subjects: (2 R)–β- d-Allopyranosyloxy-2-phenylacetonitrile; (2 S)–β- d-Allopyranosyloxy-2-phenylacetonitrile; Benzyl alcohol alloside; Biological and medical sciences; Carica papaya; Caricaceae; Caricaceae - chemistry; Chemical constitution; Chromatography, Thin Layer; Cyanogenic glycosides; d–Allose; Electrophoresis, Capillary; Fundamental and applied biological sciences. Psychology; Glycosides - chemistry; Glycosides - isolation & purification; Magnetic Resonance Spectroscopy; Mass Spectrometry; Molecular Structure; Passiflora edulis; Passifloraceae; Passifloraceae - chemistry; Plant physiology and development; Prunasin; Sambunigrin
• ISSN: 0031-9422; 1873-3700
• DOI: 10.1016/S0031-9422(02)00170-X

Leaf and stem material of Passiflora edulis (Passifloraceae) contains the new cyanogenic glycosides (2 R)–β- d-allopyranosyloxy-2-phenylacetonitrile ( 1a) and (2 S)–β- d-allopyranosyloxy-2-phenylacetonitrile ( 1b), along with smaller amounts of (2 R)–prunasin ( 2a), sambunigrin ( 2b), and the alloside of benzyl alcohol ( 4); the major cyanogens of the fruits are (2 R)–prunasin ( 2a) and (2 S)–sambunigrin ( 2b). The major cyanogenic glycoside of Carica papaya (Caricaceae) is 2a; only small amounts of 2b also are present. We were not able to confirm the presence of a cyclopentenoid cyanogenic glycoside, tetraphyllin B, in Carica papaya leaf and stem materials. In detailed 1H NMR studies of 1a/b and 2a/b, differences in higher order effects in glucosides and allosides proved to be valuable for assignment of structures in this series. The diagnostic chemical shifts of cyanogenic methine and anomeric protons in 1a/b are sensitive to anisotropic environmental effects. The assignment of C-2 stereochemistry of 1a/b was made in analogy to previous assignments in the glucoside series and was supported by GLC analysis of the TMS ethers. Leaf and stem material of Passiflora edulis (Passifloraceae) contains the cyanogenic glycosides(2 R)–β- d-allopyranosyloxy-2-phenylacetonitrile ( 1a) and (2 S)–β- d-allopyranosyloxy-2-phenylacetonitrile ( 1b) in addition to (2 R)–prunasin ( 2a) and (2 S)–sambunigrin ( 2b); the major cyanogens of the fruits are 2a and 2b. The major cyanogenic glycoside of Carica papaya (Caricaceae) is 2a; while only very small amounts of 2b are present. We were not able to confirm the presence of a cyclopentenoid cyanogenic glycoside, tetraphyllin B, in Carica papaya leaf and stem materials.