| Title: | "Positions and stereochemistry of methyl branches in the novel sex pheromone components produced by a lichen moth, Lyclene dharma dharma" |
| Author(s): | Adachi Y; Nguyen DD; Kinjo M; Makisako S; Yamakawa R; Mori K; Ando T; |
| Address: | "Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo, 184-8588, Japan" |
| DOI: | 10.1007/s10886-010-9813-3 |
| ISSN/ISBN: | 1573-1561 (Electronic) 0098-0331 (Linking) |
| Abstract: | "Female moths of Lyclene dharma dharma (Arctiidae, Lithosiinae) produce three sex pheromone components (I-III), for which we assigned the following novel chemical structures; 6-methyl-2-octadecanone (1) for I, 14-methyl-2-octadecanone (2) for II, and 6,14-dimethyl-2-octadecanone (3) for III. In the Iriomote Islands where the insects were collected, a lure including racemic 1 and 2 attracted the male moths without mixing 3. In this study for further confirmation of the plane structures, the positional isomers with a methyl branch at the 4-, 5-, 7-, 13-, or 15-position (4-8, respectively) were synthesized. The GC-MS analyses revealed that natural components I and II were best fitted with those of 1 and 2, respectively, among the methyl-2-octadecanones examined, indicating the usefulness of this analytical instrument and authentic standards for the determination of the positions of methyl branches. In field trapping tests, 4-8 could not substitute for 1 or 2, nor did these compounds inhibit the active binary lure of 1 and 2, indicating that the males strictly recognized the 2-ketones with a methyl branch at the 6- or 14-positions. Next, the absolute configurations of I and II were determined by HPLC with a normal-phased chiral column (Chiralpak AD-H), which could separate the enantiomers of both 1 and 2. The chiral HPLC analysis of a crude pheromone extract indicated that the females exclusively produced (S)-1 and (S)-2. Furthermore, a field evaluation of each enantiomer revealed that (S)-1 and (S)-2 were bioactive but (R)-1 and (R)-2 were not" |
| Keywords: | "Animals Chromatography, High Pressure Liquid Female Gas Chromatography-Mass Spectrometry Male Moths/drug effects/*metabolism Optical Phenomena Sex Attractants/*biosynthesis/chemical synthesis/*chemistry/pharmacology Stereoisomerism;" |
| Notes: | "MedlineAdachi, Yasushi Nguyen, Duc Do Kinjo, Masakatsu Makisako, Saori Yamakawa, Rei Mori, Kenji Ando, Tetsu eng 2010/07/09 J Chem Ecol. 2010 Aug; 36(8):814-23. doi: 10.1007/s10886-010-9813-3. Epub 2010 Jul 9" |
