Highly hydroxylated guaianolides of Achillea asiatica and Middle European Achillea species

• Published in: Phytochemistry (Oxford) 2001-12, Vol.58 (8), p.1189-1194
• Main Authors: Glasl, Sabine, Presser, Armin, Gunbilig, Disan, Werner, Ingrid, Narantuya, Samdan, Haslinger, Ernst, Jurenitsch, Johann, Kubelka, Wolfgang
• Format: Article
• Language: English
• Subjects: Achillea asiatica; Achillea asplenifolia; Achillea ceretanica; Achillea collina; Achillea roseoalba; Asteraceae - chemistry; Biological and medical sciences; Chemical constitution; Compositae; Europe; Fundamental and applied biological sciences. Psychology; Guaianolides; Hydroxylation; Plant physiology and development; Proazulenes; Sesquiterpene lactones; Sesquiterpenes - chemistry; Sesquiterpenes - isolation & purification; Sesquiterpenes, Guaiane
• ISSN: 0031-9422; 1873-3700
• DOI: 10.1016/S0031-9422(01)00281-3

From flower heads of Achillea asiatica (L.) Serg., three new guaianolides were isolated by repeated column chromatography and HPLC. The constitution and the stereochemistry of these new, labile compounds were determined by MS, one (1H, 13C, selective 1H-TOCSY and 1H-NOESY) and two-dimensional NMR experiments (1H, 1H-COSY, 1H, 13C-HSQC, 1H, 13C-HMBC). The substances were identified as 8α-angeloxy-2α, 4α,10β-trihydroxy-6βH,7αH, 11βH-1(5)-guaien-12,6α-olide (1), 8α-angeloxy-1β,2β:4β,5β-diepoxy-10β-hydroxy-6βH, 7αH, 11βH-12,6α-guaianolide (2) and 8α-angeloxy-4α,10β-dihydroxy-2-oxo-6βH,7αH, 11βH-1(5)-guaien-12,6α-olide (3). They were also detected in Middle European species (Achillea collina, Achillea ceretanica (2× and 4×), Achillea roseoalba, Achillea asplenifolia) by HPLC, TLC and off line MS and have not been described before. The possibility that these compounds might be products of an oxidation process is discussed. Three guaianolides were isolated from Achillea asiatica: 8α-angeloxy-2α,4α,10β-trihydroxy-6βH,7αH,11βH-1(5)-guaien-12,6α-olide (1), 8α-angeloxy-1β,2β: 4β,5β-diepoxy-10β-hydroxy-6βH,7αH,11βH-12,6α-guaianolide (2) and 8α-angeloxy-4α,10β-dihydroxy-2-oxo-6βH,7αH,11βH-1(5)-guaien-12,6α-olide (3). They were also detected in Middle European species (A. collina, A. ceretanica (2× and 4×), A. roseoalba, A. asplenifolia) by HPLC, TLC and offline MS and have not been described before.