Pheromones ipsdienol

The western pine beetle Dendroctonus brevicomis is perhaps the most destmctive insect enemy of western pine forests. The aggregation pheromone is a mixture of the terpenoid myrcene [123-35-3J (163) from the tree and the frass pheromones exo-hsevicomki [20290-99-7] (164) and frontalin [28401-39-0] (165). The Norway spmce beede Ips tppopraphus converts the tree terpenoid myrcene into the frass pheromone ipsdienol [33628-00-3] (166) and the beedes also produce 2-methyl-3-buten-2-ol [115-18-4] and rir-verbenol [473-67-6] (167), all of which are components of the aggregation pheromone. 

Attempts to investigate boll weevil (Anthonomus grandis) pheromone biosynthesis have identified isomerization, dehydration, and oxidation of the pheromone alcohols, and anticipated allylic oxidation of myrcene and limonene, but no evidence for the cyclization of acyclic precursors. The aggregation pheromones of bark beetles have been reviewed. Ips calligraphus responds to ipsdienol only in the presence of the c/5-verbenol (32) large additional concentrations of the enantiomer (l/ ,4i ,5/ )-(32) reduce beetle response. 5-(-)-Ipsenol, the pheromone of Ips grandicollis, increases the response of /. avulsus to its own pheromone ipsdienol. ... 

Byers J. A. (1982) Male specific conversion of the host plant compound, myrcene, to the pheromone, (+) ipsdienol, in the bark beetle, Dendroctonus brevicomis. J. Chem. Ecol. 8, 363-371. 

Hall G. M., Tittiger C., Andrews G., Mastick G., Kuenzli M., Luo X., Seybold S. J. and Blomquist G. J. (2002) Male pine engraver beetles, Ipspini, synthesize the monoterpenoid pheromone ipsdienol de novo in midgut tissue. Naturwissenschaften (in press). 

Kubo andNakatsu (11) separated the racemic pheromone ipsdienol into pure enantiomers using an indirect approach. ( )-Ipsdienol was derivatized with (+)-a-methoxy-a-(trifluoromethyl)-phenylacetic acid (MTPA) to yield a mixture of diastereoisomers (Fig. 19), which were separated by conventional normal phase preparative HPLC using a nucleosil silica column with product recycling (see Subheading 2.3.4.). After seven cycles the diastereomers were... 

Sandstrom R Ginzel MD, Bearfield JC, Welch WH, Blomquist GJ, Tittiger C (2008) Myrcene hydroxylases do not determine enantiomeric composition of pheromonal ipsdienol in Ips spp. J Chem Ecol 34 1584-1592... 

Mustaparta, H., Angst, M. E. and Lanier, G. N. (1977) Responses of single receptor cells in the pine engraver beetle Ips pini (Say) (Coleoptera Scolytidae) to its aggregation pheromone ipsdienol and the aggregation inhibitor, ipsenol. J. comp. Physiol., 121, 343-7. 

This distinction clarifies the surprising differential sensitivity of male and female 7. paraconfusus to components of their pheromone and to that of I. pint. Males and females are equally sensitive to their natural pheromone and to its component, (+ )ipsdienol, over a wide range of concentrations. However, females are significantly more sensitive to pheromonal ( + )ipsdienol than to allomonal (-)ipsdienol (the pheromone of I. pini), whereas males are more sensitive to allomonal (- )ipsdienol than to their own pheromonal (+ )ipsdienol (Light and Birch, 1982). There is a clear adaptive advantage for males to locate new host material quickly and to avoid resources occupied by /. pini, unless nothing else is available, since if the two species do co-colonize a resource, the reproductive potentials of both are reduced. This premium on selection of unoccupied resources underlies the high sensitivity of males to allomonal ipsdienol. The interruption of response in 7. paraconfusus by verbenone from D. brevicomis may have a similar basis. 

A number of new and asymmetric syntheses of (S)-(-)-ipsenol (34) and (S)-(+)-ipsdienol (35), the pheromone of Ips bark beetles, were reported. Scheme 49 summarizes the synthesis of ipsenol by Riedeker and Steiner [75], which enabled them to prepare 56 g of (S)-34. They employed chiral auxiliary B derived from D-glucose. 

Evidence for de novo synthesis of pheromone components was obtained by showing that labeled acetate and mevalonate were incorporated into ipsdienol by male Ips pini [103,104]. Similarly, labeled acetate and other labeled intermediates were shown to be incorporated into frontalin in a number of Dendroctonus species [105]. Possible precursors to frontalin include 6-methyl-6-hep-ten-2-one, which was incorporated into frontalin by D. ruffipennis [106]. The precursor 6-methyl-6-hepten-2-one also was shown to be converted to bre-vicomin in the bark beetle, Dendroctonus ponderosae [107]. In addition, the expression patterns of HMG-CoA reductase and HMG-CoA synthase are tightly correlated with frontalin production in Dendroctonus jeffreyi [108, 109]. A geranyl diphosphate synthase cDNA from I. pini was also isolated, functionally expressed, and modeled [110]. These data indicate that the de novo isoprenoid biosynthetic pathway is present in bark beetles. A variety of other monoterpene alcohols such as myrcenol, pityol, and sulcitol are probably synthesized through similar pathways [111]... 

FIGURE 2 Pheromone structures of the American cockroach (periplanone B), the brownbanded cockroach (supellapyrone), bark beetles (ipsdienol enantiomers), and the cabbage looper moth (six acetates). 

In the reactions with mono- and 1,2-disubstituted olefins, however, no ene product was obtained. This limitation has been overcome by the use of vinylic sulfides and selenides instead of mono- and 1,2-disubstituted olefins. With these substrates, the ene products are obtained with comparably high enantioselectivity and high diastereoselectivity [15]. The synthetic utility of the vinylic sulfide and selenide is shown in the synthesis of enantiopure (R)-(-)-ipsdienol, an insect-aggregation pheromone (Scheme 8C.4) [16]. 

Practical use of pheromones started in 1978. That year we used 110.000 trap-trees sprayed with an insecticide (Lindane). The first year we used one dispenser with an initial loading of 70 mg cis-verbenol and 10 mg ipsdienol. A second dispenser was loaded with 100 mg methylbutenol. In 1979 we adjusted the loading and used only one dispenser containing all 3... 

Seybold S. J., Quilici D. R., Tillman J. A., Vanderwel D., Wood D. L. and Blomquist G. J. (1995) De novo biosynthesis of the aggregation pheromone components ipsenol and ipsdienol by the pine bark beetles Ips paraconfusus Lanier and Ipspini (Say) (Coleoptera Scolytidae). Proc. Natl. Acad. Sci. USA 92, 8393-8397. 

Figure 6.9 Examples of pheromone components of bark beetles (Scolytidae) and ambrosia beetles (Scolytidae and Platypodidae) classified by likely biosynthetic origin (based on Francke and Schulz, 1999). (A) References for identification and/or behavioral activity of isoprenoid pheromone compounds are as follows-. 2-methyl-3-buten-2-ol (Bakke efa/., 1977 Giesen etal., 1984 Klimetzek etal., 1989a Lanne etal., 1989), 3-methyl-3-buten-1-ol (Stoakley etal., 1978 Bowers and Borden, 1990 Bowers etal, 1991 Zhang efa/., 2000), 3-methyl-1-butanol (Renw ick etal, 1977), 3-hydroxy-3-methylbutan-2-one (Francke and Heeman, 1974 Francke etal 1974), ipsenol and ipsdienol...

Figure 6.11 Biosyntheses of isoprenoid pheromone components by bark and ambrosia beetles from host conifer monoterpenes. (A) Conversion by the male California fivespined ips, Ips paraconfusus Lanier (Coleoptera Scolytidae), of myrcene from the xylem and phloem oleoresin of ponderosa pine, Pinus ponderosa Laws., to (4S)-(+)-ipsdienol and (4S)-(-)-ipsenol, components of the aggregation pheromone (Hendry et al., 1980). (B) Conversion by male and female I. paraconfusus of (1 S,5S)-(-)-a-pinene (2,6,6-trimethyl-bicyclo[3.1,1]hept-2-ene) from the xylem and phloem oleoresin of P. ponderosa to (1 S,2S,5S)-(+)-c/s-verbenol (c/s-4,6,6-trimethyl-bicyclo[3.1,1]hept-3-en-2-ol), an aggregation pheromone synergist and of (1 R,5R)-(+)-a-pinene to (1 fl,2S,5fl)-(+)-frans-verbenol (frans-4,6,6-trimethyl-bicyclo[3.1,1]hept-3-en-2-ol), a compound of unknown behavioral activity for /. paraconfusus. Male and female western pine beetle, Dendroctonus brevicomis LeConte (Coleoptera Scolytidae), convert (1 S,5S)-(-)-a-pinene to (1S,2ft,5S)-(-)-frans-verbenol, an aggregation pheromone interruptant and (1R,5R)-(+)-a-pinene to (1 R,2S,5R)-(+)-frans-verbenol, a compound of...

Fish R. H., Browne L. E., Wood D. L. and Hendry L. B. (1979) Pheromone biosynthetic pathways conversions of deuterium-labelled ipsdienol with sexual and enantioselectivity in Ips paraconfusus. Tetrahedron Lett. 17, 1465-1468. 

Fish R. H., Browne L. E. and Bergot B. J. (1984) Pheromone biosynthetic pathways conversion of ipsdienone to (-)-ipsdienol, a mechanism for enantioselective reduction in the male bark beetle, Ips paraconfusus. J. Chem. Ecol. 10, 1057-1064. 

Ivarsson P., Schlyter F. and Birgersson G. (1993) Demonstration of de novo pheromone biosynthesis in Ips duplicatus (Coleoptera Scolytidae) inhibition of ipsdienol and E-myrcenol production by compactin. Insect Biochem. Molec. Biol. 23, 655-662. 

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