Female sex pheromone

Dizinno G., Whitney G. and Nyby J. (1978). Ultrasonic vocalisation by male mice (Mus musculus) to female sex pheromone experiential determinants. Behav Biol 22, 104-113. 

Sorensen P.W., Hara T.J., Stacey N.E. and Goetz F. (1988). F-prostaglandins function as potent olfactory stimulants that comprise the post-ovulatory female sex pheromone in goldfish. Biol Reprod 39, 1039-1050. 

Scheme 7 summarizes the synthesis of (7JR,llS)-7,ll-dimethylheptadecane (1), the female sex pheromone of the spring hemlock looper (Lambdina athasaria) by Mori [ 18]. Enantiopure alkanes are usually synthesized by coupling enantio-pure building blocks derived from natural products or compounds prepared by asymmetric synthesis. Even among hydrocarbons, chirality is very important for pheromone activity, and in this particular case meso-1 was bioactive, while neither (7R,11R)-1 nor (7S,11S)-1 showed bio activity. 

Two new syntheses of bombykol (6), the female sex pheromone of the silkworm moth (Bombyx mori), were reported [22,23]. Scheme 11 shows Negishi s synthesis of 6 based on organoborane chemistry [22], and Uenishi s synthesis of 6 based on palladium and nickel catalyses is summarized in Scheme 12 [23]. Both syntheses afforded bombykol of >98% purity. 

In 1992, nitrate esters 10 and 11 were identified as the female sex pheromone of the cotton leaf perforator (Bucculatrix thurberiella) [26]. Synthesis of (Z)-9-tetradecenyl nitrate (10) and (Z)-8-tridecenyl nitrate (11) is shown in Scheme 16 [26]. A 100 2 blend of 10 and 11 is highly attractive for male B. thurberiella. 

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. 

Z,9S,10 )-9,10-Epoxyhenicos-6-ene (13) is the female sex pheromone of moths such as ruby tiger moth (Phragmatobiafuliginosa), fruit-piercing moth (Oraesia excavata), and painted apple moth (Teia anartoides). Scheme 23 summarizes Shi s synthesis of 13 based on Sharpless asymmetric dihydroxylation (AD) [36]. Mori synthesized 13 employing lipase to prepare A (Scheme 24) [37]. Alkylation of the acetylide anion C was possible neither with tosylate nor with iodide, but triflate B could alkylate C to give D. 

Posticlure [(6Z,9Z,llS,12S)-ll,12-epoxy-6,9-henicosadiene, 14] is the female sex pheromone of the tussock moth, Orgyia postica. Wakamura s first synthesis of 14 was achieved by employing Sharpless asymmetric epoxidation, and the final product was of 59% ee [38]. Mori prepared 14 of high purity as shown in Scheme 25 basing on asymmetric dihydroxylation (AD) [39]. Kumar also published an AD-based synthesis of 14 [40], which was more lengthy and less efficient than Mori s [39]. 

Several female sex pheromones of pine bast scales were identified and synthesized. Scheme 29 summarizes Mori s synthesis of the pheromone [( )-18] of the Israeli pine bast scale (Matsucoccus josephi) [51]. Enzymatically prepared... 

Scheme 32 summarizes Matteson s synthesis of serricornin [(4S,6S,7S)-21], the female sex pheromone of the cigarette beetle (Lasioderma serricorne) via boronic esters [55]. Due to the highly stereoselective nature of boronic ester chemistry, this synthesis of 21 was quite efficient. 

Scheme 56 summarizes Mori s synthesis of (S)-vesperal (38), the female sex pheromone of the longhorn beetle (Vesperus xatarti) [85]. (F)-Limonene yielded (S)-38 by utilizing organoselenium chemistry. 

R,4R)-Supellapyrone (41) is the female sex pheromone of the brown banded cockroach (Supella longipalpa). Scheme 59 summarizes Mori s synthesis of 41 [89].Enzymatic desymmetrization of meso-B to give (2R,4S)-C and Reformatsky-type cyclization of D to furnish E were the key steps. 

Taxonomy of Moths and Overview of Their Female Sex Pheromones. .. 53... 

Fig. 2 Taxonomy and pheromone studies of insects in the superfamily of Noctuoidea. The numbers before and after + in parenthesis of each group indicates the total number of species whose female sex pheromone and male attractant have been reported respectively. Each mark after the group name indicates that some species within the group produces a pheromone component of Type I ( with a common functional group, with a novel functional group), Type II (A), or others )...

LeMaster, M.P. and Mason, R.T. (2001) Evidence for a female sex pheromone mediating male trailing behavior in the red-sided garter snake, Thamnophis sirtalis parietalis. Chemoecology 11, 149-152. 

This long-chain unsaturated ester serves as one component of a mnlticomponent female sex pheromone for 140 species of moths as well as the Asian elephant. This is nnlikely to cause any real confnsion in nature. On the one hand, the 140 species of moths keep ont of each other s way and out of the elephant s way by varying the nature and relative concentrations of other components in the multicomponent pheromone. On the other hand, the male elephant is not likely to detect the extremely small amonnts of this pheromone released by female moths. Chemistry aside, there are other obvions difficnlties in moths mating with elephants in the wild. 

Leucomalure [15, a mixture of (3Zy6R y7S y9R ylOS ) and (3Z,6i, 7S, 9S, 10i )-ns-6,7-ds-9,10-diepoxy-3-henicosene] is the female sex pheromone of the Satin moth (Leucoma salicis) [41]. Its racemic and diastereomeric mixture... 

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