| Title: | 3-Acetoxy-fatty acid isoprenyl esters from androconia of the ithomiine butterfly Ithomia salapia |
| Author(s): | Mann F; Szczerbowski D; de Silva L; McClure M; Elias M; Schulz S; |
| Address: | "Institute of Organic Chemistry, Technische Universitat Braunschweig, Hagenring 30, 38106 Braunschweig, Germany. Institut de Systematique Evolution Biodiversite, Centre National de la Recherche Scientifique, MNHN, Sorbonne Universite, EPHE, Universite des Antilles, 45 rue Buffon, CP 50, 75005 Paris, France. Laboratoire Ecologie, Evolution, Interactions des Systemes Amazoniens (LEEISA), Universite de Guyane, CNRS, IFREMER, 97300 Cayenne, France" |
| ISSN/ISBN: | 1860-5397 (Print) 1860-5397 (Electronic) 1860-5397 (Linking) |
| Abstract: | "Male ithomiine butterflies (Nymphalidae: Danainae) have hairpencils on the forewings (i.e., androconia) that disseminate semiochemicals during courtship. While most ithomiines are known to contain derivatives of pyrrolizidine alkaloids, dihydropyrrolizines, or gamma-lactones in these androconia, here we report on a new class of fatty acid esters identified in two subspecies, Ithomia salapia aquinia and I. s. derasa. The major components were identified as isoprenyl (3-methyl-3-butenyl) (Z)-3-acetoxy-11-octadecenoate, isoprenyl (Z)-3-acetoxy-13-octadecenoate (12) and isoprenyl 3-acetoxyoctadecanoate (11) by GC/MS and GC/IR analyses, microderivatizations, and synthesis of representative compounds. The absolute configuration of 12 was determined to be R. The two subspecies differed not only in the composition of the ester bouquet, but also in the composition of more volatile androconial constituents. While some individuals of I. s. aquinia contained ithomiolide A (3), a pyrrolizidine alkaloid derived gamma-lactone, I. s. derasa carried the sesquiterpene alpha-elemol (8) in the androconia. These differences might be important for the reproductive isolation of the two subspecies, in line with previously reported low gene exchange between the two species in regions where they co-occur. Furthermore, the occurrence of positional isomers of unsaturated fatty acid derivatives indicates activity of two different desaturases within these butterflies, Delta9 and Delta11, which has not been reported before in male Lepidoptera" |
| Keywords: | fatty acid esters mass spectrometry mimicry pheromones pyrrolizidine alkaloids; |
| Notes: | "PubMed-not-MEDLINEMann, Florian Szczerbowski, Daiane de Silva, Lisa McClure, Melanie Elias, Marianne Schulz, Stefan eng Germany 2020/12/08 Beilstein J Org Chem. 2020 Nov 16; 16:2776-2787. doi: 10.3762/bjoc.16.228. eCollection 2020" |
