Isolation and characterisation of 13 pterosins and pterosides from bracken (Pteridium aquilinum (L.) Kuhn) rhizome

• Published in: Phytochemistry (Oxford) 2016-08, Vol.128, p.82-94
• Main Authors: Mohammad, Rizgar Hassan, Nur-e-Alam, Mohammad, Lahmann, Martina, Parveen, Ifat, Tizzard, Graham J., Coles, Simon J., Fowler, Mark, Drake, Alex F., Heyes, Derren, Thoss, Vera
• Format: Article
• Language: English
• Subjects: Animals; Bracken pterosins; Circular dichroism; Dennstaedtiaceae; Diabetes Mellitus - drug therapy; Glycosides - chemistry; Glycosides - isolation & purification; Indans - chemistry; Indans - isolation & purification; Norsesquiterpenes; Nuclear Magnetic Resonance, Biomolecular; Pteridium - chemistry; Pteridium aquilinum; Pterosides; Pterosins A and B; Rhizome - chemistry; Sesquiterpenes - chemistry; Sesquiterpenes - isolation & purification; Sesquiterpenes - pharmacology; Sesquiterpenoids; SGLT1 and GLUT2 transporters
• ISSN: 0031-9422; 1873-3700; 1873-3700
• DOI: 10.1016/j.phytochem.2016.05.001

Systematic phytochemical investigations of the underground rhizome of Pteridium aquilinum (L.) Kuhn (Dennstaedtiaceae) afforded thirty-five pterosins and pterosides. By detailed analysis of one- and two-dimensional nuclear magnetic resonance spectroscopy, circular dichroism (CD) and high-resolution mass spectrometric data, thirteen previously undescribed pterosins and pterosides have been identified. Interestingly, for the first time 12-O-β-D-glucopyranoside substituted pterosins, rhedynosides C and D, and the sulfate-containing pterosin, rhedynosin H, alongside the two known compounds, histiopterosin A and (2S)-pteroside A2, were isolated from the rhizomes of subsp. aquilinum of bracken. In addition, six-membered cyclic ether pterosins and pterosides, rhedynosin A and rhedynoside A, are the first examples of this type of pterosin-sesquiterpenoid. Additionally, the three previously reported compounds (rhedynosin I, (2S)-2-hydroxymethylpterosin E and (2S)-12-hydroxypterosin A) were obtained for the first time from plants as opposed to mammalian metabolic products. Single crystal X-ray diffraction analysis was applied to the previously undescribed compounds (2R)-rhedynoside B, (2R)-pteroside B and (2S)-pteroside K, yielding the first crystal structures for pterosides, and three known pterosins, (2S)-pterosin A, trans-pterosin C and cis-pterosin C. Rhedynosin C is the only example of the cyclic lactone pterosins with a keto group at position C-14. Six selected pterosins ((2S)-pterosin A, (2R)-pterosin B and trans-pterosin C) and associated glycosides ((2S)-pteroside A, (2R)-pteroside B and pteroside Z) were assessed for their anti-diabetic activity using an intestinal glucose uptake assay; all were found to be inactive at 300 μM. Thirteen previously undescribed pterosins and pterosides were isolated from bracken rhizomes in north of Wales. Their structures were elucidated using NMR spectroscopic and high resolution FT-ICR-MS data. [Display omitted] •35 pterosins, 13 previously undescribed compounds in British bracken rhizomes.•Single crystal X-ray obtained for 3 pterosins and 3 pterosides.•Anti-diabetic activity of pterosins was not observed at concentration 300 μM.•Diverse structural features previously unreported for pterosins and pterosides.