Lymantria dispar pheromone

R,8S)-(+)-Disparlure (12) is the female sex pheromone of the gypsy moth (Lymantria dispar). Advent of Sharpless asymmetric dihydroxylation (AD) allowed several new syntheses of 12 possible. Sharpless synthesized 12 as shown in Scheme 17 [27]. Scheme 18 summarizes Ko s synthesis of 12 employing AD-mix-a [28]. He extended the carbon chain of A by Payne rearrangement followed by alkylation of an alkynide anion with the resulting epoxide to give B. Keinan developed another AD-based synthesis of 12 as shown in Scheme 19 [29]. Mit-sunobu inversion of A to give B was the key step, and the diol C could be purified by recrystallization. 

Some lepidopteran species secret methyl-branched chemicals for their sexual communication. These have been abbreviated with Me to indicate the position of the methyl group. Disparlure (Me2,epo7-18 H) is a well-known pheromone identified from Lymantria dispar [3] and two other species in the same genus, L.fumida [95] and L. monacha [96]. L. monacha also secrets an... 

A study using the gypsy moth, Lymantria dispar, illustrates the overall pathways involved in production of epoxide pheromone components (Fig. 3) [77]. This insect uses disparlure, Me2,epo7-18 H, as a pheromone component. In-... 

In moths, it was discovered in Helicoverpa zea that a peptide produced in the subesophageal ganglion portion of the brain complex regulates pheromone production in female moths (19). This factor has been purified and characterized in three species, Helicoverpa zea (20), Bombyx mori (21, 22), and Lymantria dispar (23). They are all a 33- or 34-amino acid peptide (named pheromone biosynthesis activating neuropeptide, PBAN) and have in common an amidated C-terminal 5-amino acid sequence (FXPRL-amide), which is the minimum peptide fragment required for pheromon-tropic activity. In the redbanded leafroller moth, it was shown that PBAN from the brain stimulates the release of a different peptide from the bursae copulatrix that is used to stimulate pheromone production in the pheromone gland found at the posterior tip of the abdomen (24). 

Kuenen, L. P. S. and Carde, R. T. (1993) Effects of moth size on velocity and steering during upwind flight toward a sex pheromone source by Lymantria dispar (Lepidoptera Lymantriidae). Journal of Insect Behavior 6 177-193. 

Kowcun A., Honson N. and Plettner E. (2001) Olfaction in the gypsy moth, Lymantria dispar, effect of pH, ionic strength, and reductants on pheromone transport by pheromonebinding proteins. J. Biol. Chem. 276, 44770 -4776. 

Plettner E., Lazar J., Prestwich E. G. and Prestwich G. D. (2000) Discrimination of pheromone enantiomers by two pheromone binding proteins from the gypsy moth Lymantria dispar. Biochemistry 39, 8953-8962. 

Jurenka R. A. and Subchev M. (2000) Identification of cuticular hydrocarbons and alkene precursor to the pheromone in hemolymph of the female gypsy moth, Lymantria dispar. Arch. Insect Biochem. Physiol. 43, 108-115. 

Figure 3.7 Production of the sex pheromone in the gypsy moth, Lymantria dispar. The oenocyte cells located in the abdomen biosynthesize the alkene hydrocarbon precursor to the pheromone, 2me-Z7-18 Hc. It is transported through the hemolymph by lipophorin. The alkene is taken up by pheromone gland cells where it is acted upon by an epoxidase to produce the pheromone disparlure, 2me-18 7,8Epox.

Hollander A. L. and Yin C.-M. (1985) Lack of humoral control in calling and pheromone release by brain, corpora cardiaca, corpora allata and ovaries of the female gypsy moth, Lymantria dispar (L.). J. Insect Physiol. 31, 159-163. 

Tang J. D., Charlton R. E., Carde R. T. and Yin C.-M. (1987) Effect of allatectomy and ventral nerve cord transection on calling, pheromone emission and pheromone production in Lymantria dispar. J. Insect Physiol. 33, 469-476. 

Thyagaraja B. S. and Raina, A. K. (1994) Regulation of pheromone production in the gypsy moth, Lymantria dispar, and development of an in vitro bioassay. J. Insect Physiol. 40, 969-974. 

Vogt R. G., Koehne A. C., Dubnau J. T. and Prestwich G. D. (1989) Expression of pheromone binding proteins during antennal development in the gypsy moth Lymantria dispar. J. Neurosci. 9, 3332-3346. 

Diversity in the structure and proportion of pheromone components is mirrored in the diversity of the proteins from the olfactory system. A specialized olfactory system is responsible for distinguishing the pheromone from other odorants in the environment. The high precision of the pheromone olfactory system becomes apparent when we compare closely related species whose pheromones differ in subtle ways. For example, Heliothis species have the same unsaturated aldehyde as the major pheromone component, but their pheromone signals differ in the structure and proportion of minor components (Table 16.1). Another example is seen with the gypsy moth (Lymantria dispar) and nun moth (Lymantria monacha), both of which respond to la. The blend produced by the nun moth consists mostly of lb, which is a powerful behavioral antagonist in the gypsy moth and is behaviorally inactive in the nun moth (Hansen, 1984). Stereochemical features play an important role in the molecular recognition of pheromone components. 

Grant G. G., Langevin D., Liska J., Kapitola P. and Chong J. M. (1996) Olefin inhibitor of gypsy moth, Lymantria dispar, is a synergistic pheromone component of nun moth, L. monacha. Naturwissenschaften 83, 328-330. 

Jurenka, R. A., Subchev, M Abad, J.-L., Choi, M.-J. and Fabrias, G. (2003). Sex pheromone biosynthetic pathway for disparlure in the gypsy moth, Lymantria dispar. Proc. Natl. Acad. Sci. USA, 100, 809-814. 

The occurrence of hydrocarbons (usually mono- and di-alkenes) with an epoxide function group have been reported usually as sex attractants. The sex attractant of the female gypsy moth, Lymantria dispar, was identified as the C18 2-methyl alkane derivative cis-7,S-epoxy-2-methyloctadecane (Bierl et al 1972). For the housefly, M. domestica, a major sex pheromone component is the C23 -alkane epoxide d.v-9,1O-cpoxytricosane (Uebel et al 1978) with a lesser quantity of 9,10-epoxyheptacosane (Mpuru et al., 2001). 

---