Structure revision of xanthalongin and further sesquiterpene lactones from flowers of Arnica longifolia

In addition to the helenanolide and xanthanolide type sesquiterpene lactones previously isolated from A. longifolia D.C. Eaton, we report on 13 further sesquiterpene lactones (7 helenanolides, 1 xanthanolide, 3 1,5-guaianolides, 1 1,5-cis-guaianolide and 1 eudesmanolide) occurring in the flowerheads of this species. The structure of xanthalongin is revised to a 10β-methyl configurated xanthanolide on the basis of new NMR spectral evidence. Furthermore, the 1,5-cis-guaianolide 2-O-acetylarnimollin, in contrast with our previous assignment, possesses a 2α-O-acyl configuration. A sesquiterpene lactone pattern as diverse as that of A. longifolia consisting of 1,5-trans-guaianolides and pseudoguaianolides (helenanolides), 1,5-cis-guaianolides and xanthanolides as well as eudesmanolides, which are postulated to be derived from three different biogenetic pathways, is particularly remarkable.