Sex pheromones biosynthetic pathways

Martinez T., Fabrias G. and Camps F. (1990) Sex pheromone biosynthetic pathway in Spodoptera littoralis and its activation by a neurohormone. J. Biol. Chem. 265, 1381— 1387. 

Fabrias G., Barrot M. and Camps F. (1995) Control of the sex pheromone biosynthetic pathway in Thaumetopoea pityocampa by the pheromone biosynthesis activating neuropeptide. Insect Biochem. Mol. Biol. 25, 655-660. 

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. 

FIGURE 3 Pheromone biosynthetic pathways commonly used in moth sex pheromone glands to produce precursors for specific blends of acetates, alcohols, or aldehydes. Cascades of precursors are produced by combinations of unique A- -desaturases and limited chain-shortening steps. The six precursors for the cabbage looper blend (Figure 2) are in boldface type. 

FIGURE 4 Proposed model for the interaction of PBAN with a receptor on the sex pheromone gland of a corn earworm female, and the resulting stimulation of acetyl-CoA carboxylase of the pheromone biosynthetic pathway. 

Sex pheromone component ratio in the cabbage looper moth altered by a mutation affecting the fatty acid chain-shortening reactions in the pheromone biosynthetic pathway. Insect Biochemistry and Molecular Biology 24 373-381. 

Jurenka R. A., Haynes K. F., Adlof R. O., Bengtsson M. and Roelofs W. L. (1994) Sex pheromone component ratio in the cabbage loopermoth altered by a mutation affecting the fatty acid chain-shortening reactions in the pheromone biosynthetic pathway. Insect Biochem. Mol. Biol. 24, 373-381. 

Fig. (6). Blattodean pheromone biosynthetic pathways utilize fatty acid biosynthesis from malonyl-CoA and methylmalonyl- CoA substrates followed by cytochrome P-450-mediated decarboxylation, hydroxylation, and oxidation. The hydroxylation step is regulated by JH III (adapted from ref. L72bJ, for Blattella germanica sex...

Abstract Pheromones are utilized by many insects in a complex chemical communication system. This review will look at the biosynthesis of sex and aggregation pheromones in the model insects, moths, flies, cockroaches, and beetles. The biosynthetic pathways involve altered pathways of normal metabolism of fatty acids and isoprenoids. Endocrine regulation of the biosynthetic pathways will also be reviewed for the model insects. A neuropeptide named pheromone biosynthesis activating neuropeptide regulates sex pheromone biosynthesis in moths. Juvenile hormone regulates pheromone production in the beetles and cockroaches, while 20-hydroxyecdysone regulates pheromone production in the flies. 

Fig. 3 Proposed biosynthetic pathways for the production of the sex pheromone components in the indicated insects. Common mechanisms include fatty acid synthesis, desaturation, chain elongation, and decarboxylation...

Figure 3.2 A. Possible biosynthetic pathways for producing the sex pheromone components Z9-14 OAc and Z9,E12-14 OAc in the almond moth. The Z9-14 CoA and Z9,E12-14 CoA derivatives are reduced and acetylated to make the acetate esters. B. The biosynthetic pathway as determined by deuterium labeling studies presented in Figure 3.3.

Figure 3.4 Biosynthetic pathways for producing the sex pheromone components of Helicoverpa zea and Helicoverpa assulta. The CoA derivatives indicated with an arrow are reduced to aldehydes. The unlabeled and labeled aldehyde amounts for each pheromone component are shown in the graphs on the right. The y-axis indicates ng/gland for each aldehyde indicated in the biosynthetic pathway. The graphs indicate unlabeled and labeled aldehyde amounts after application of D3-16 acid (left bars) and D3-18 acid (right bars). No label was found in Z7-16 Ald when D3-16 acid was applied to glands of H. zea. No label was found in either Z9-16 Ald or Z11-16 Ald when D3-18 acid was applied to glands of H. assulta.

Ando T., Hase T., Arima R. and Uchiyama M. (1988) Biosynthetic pathway of bombykol, the sex pheromone of the female silkworm moth. Agric. Biol. Chem. 52, 473-478. 

Jurenka R. A. (1997) Biosynthetic pathway for producing the sex pheromone component (Z,E)-9,12-tetradecadienyl acetate in moths involves a delta-12 desaturase. Cell. Mol. Life Sci. 53, 501-505. 

Ono A., Imai T., Inomata S.-I., Watanabe A. and Ando T. (2002) Biosynthetic pathway for production of a conjugated dienyl sex pheromone of a plusiinae moth, Thysanoplusia intermixta. Insect Biochem. Mol. Biol. 32, 701-708. 

Sex pheromones in the Lepidoptera are multi-component mixtures consisting mostly of olefinic compounds possessing a terminal aldehyde, alcohol, or acetate moiety. Besides functional group differences, the constituents of lepidopteran sex pheromones vary in hydrocarbon chain length and in the specific number, location, and geometry of double bonds. These chemical structures are formed in biosynthetic pathways involving a limited number of enzymatic steps believed to use fatty-acyl thioesters of coenzyme A (acyl-CoA) as substrates. Key reactions are desaturation, limited [3-oxidation, and a small number of terminal functional group modifications (reviewed in Chapter 3). 

P. americana (Persoons et al., 1979 Still, 1979), and only one additional female volatile sex pheromone has been identified outside the Periplaneta group, in S. longipalpa (Charlton et al., 1993 Leal et al., 1995). Obviously, more cockroach sex pheromones need to be identified to provide material for comparative studies on biosynthetic pathways and their endocrine and neural control. It would be of particular interest to identify sex pheromones of solitary, nocturnal cockroach species that do not associate with humans. They are most likely to communicate with volatile sex pheromones over longer distances. Indeed, field studies have shown that calling occurs in a variety of tropical species representing two of the largest cockroach families, Blattellidae and Blaberidae (Schal and Bell, 1985). 

Eliyahu, D., Nojima, S., Mori, K. and Schal, C. (2007). New contact sex pheromone components of the German cockroach, Blattella germanica, predicted from the proposed biosynthetic pathway. J. Chem. Ecol., 34, 229-237. 

In the approximately thirty years since the first identification of an insect sex pheromone (1), interest in the chemistry of these compounds has increased dramatically. This is due both to academic interest and to the use of these compounds for insect monitoring and control. More recently, the biochemistry of these compounds has been studied (2-3). In this paper, we discuss the biosynthesis of a class of these compounds and consider some of the key enzymes involved in the biosynthetic pathway. 

Fig, ( 8). Acetate biosynthetic pathway leading to fatty acids and polyketides. Structures of Lepidopteran sex pheromones can be explained as being derived from poly-P-keto chains, formed by coupling of acclic acid (C2) units via condensation reactions. Adapted from ref. f287]... 

Figure 2. Biosynthetic pathway leading to the major active component of the T, ni sex pheromone.

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