Periplaneta Periplanone

In 1952, it was reported that a constituent of excretions from female American cockroaches of the species Periplaneta ameri-cana is an extraordinarily potent sex pheromone.1 Early attempts to isolate and characterize the active compounds were hampered because individual cockroaches store only minute amounts of the pheromone ( 1 pg), and a full 25 years elapsed before Persoons et al. reported the isolation of two extremely active compounds, periplanones A and B.2 The latter substance is present in larger relative measure and its germacranoid structure (1, without stereochemistry) was tentatively assigned on the basis of spectroscopic data. Thus, in 1976, the constitution of periplanone B was known but there remained a stereochemical problem of a rather serious nature. Roughly three years intervened between the report of the gross structure of periplanone B and the first total synthesis of this substance by W. C. Still at Columbia.3... 

Based on the successful series of transformations summarized in Scheme 1, Schreiber and Santini developed an efficient and elegant synthesis of periplanone B (1),8 the potent sex pheromone of the American cockroach, Periplaneta americana. This work constitutes the second total synthesis of periplanone B, and it was reported approximately five years after the landmark periplanone B synthesis by W.C. Still9 (see Chapter 13). As in the first synthesis by Still, Schreiber s approach to periplanone B takes full advantage of the facility with which functionalized 5-cyclodecen-l-one systems can be constructed via anionic oxy-Cope rearrangements of readily available divinylcyclohexanols.5 7 In addition, both syntheses of periplanone B masterfully use the conformational preferences of cyclo-decanoid frameworks to control the stereo- and regiochemical course of reactions carried out on the periphery of such ring systems.10... 

Periplanone-D Periplaneta americana 9 Periplanetafuliginosa 9 Digestive tract"... 

In addition to their role in orientation behavior, the periplanones may participate in reproductive isolation among sympatric Periplaneta species. Periplanone-A from P. americana attracts Periplaneta australasiae. Periplanone-B, and possibly some other components, inhibits attraction of male P australasiae (Seelinger, 1985b). Two other periplanones, periplanone-C (3 Table 6.2) and periplanone-D (4 Table 6.2), have been isolated from P. americana (Biendl et al, 1989 Takahashi et al,... 

More than 20 years after their original isolation in 1952, the chemical structures of periplanone-A and periplanone-B from P. americana have been completely identified. Volatile pheromones of several other Periplaneta spp. have also been... 

Biendl, M., Hauptmann, H. and Sass, H. (1989). Periplanone Di and periplanone D2 two new biologically active germacranoid sesquiterpenes from Periplaneta americana. Tetrahedron Letters 30 2367-2368. 

Nishii, Y Watanabe, K., Yoshida, T., Okayama, T Takahashi, S. and Tanabe, Y. (1997). Total synthesis of (—)-periplanones C and D. Their pheromonal activities against three Periplaneta species. Tetrahedron 53 7209-7218. 

Okada, K., Mori, M., Shimazaki, K. and Chuman, T. (1990b). Behavioral responses of male Periplaneta americana L. to female sex pheromone components, periplanone-A and periplanone-B. Journal of Chemical Ecology 16 2605-2614. 

W. J. (1976). Sex pheromones of the American cockroach, Periplaneta americana a tentative structure of periplanone-B. Tetrahedron Letters 24 2055-2058. 

Seelinger, G. and Gagel, S. (1985). On the function of sex pheromone components in Periplaneta americana improved odour source localization with periplanone-A. 

Takahashi, S., Takegawa, H., Takabayashi, J., Abdullah, M., Fatimah, A. S. and Mohamed, M. (1988a). Sex pheromone activity of synthetic periplanone-B in male cockroaches of genera Periplaneta and Blatta. Journal of Pesticide Science 13 125-127. 

Periplaneta americana to periplanone B, a synthetic component of the female sex pheromone. Journal of Chemical Ecology 7 969-979. 

The names periplanone-A and periplanone-B were first coined by Ritter and Persoons in 1974 at the International Congress of Pesticide Chemistry in Helsinki, in a general paper on pheromone research in the Netherlands. In this paper the isolation of a number of pheromones were described, including the two peripla-nones, both sex pheromones, present in the excreta of the female American cockroach, Periplaneta americana. The elementary formulae of these two sesquiterpenoids, C15H20O2 and C15H20O3, were given and the carbon skeleton of periplanone-B, a germacrane derivative, was revealed. Unfortunately, we were informed, one year after the... 

Periplanone-A and periplanone-B have been found to occur in a ratio of 1 10 in faecal material of Periplaneta americana, but only periplanone-B has been found in intestinal tracts. This could suggest that periplanone-B is a genuine sex pheromone, whereas periplanone-A could be a biologically active transformation product, which in turn can isomerize into a more stable but inactive compound. We have given hypothetical schemes for such a transformation elsewhere (32,40). 

Recently electrophysiological experiments by Sasz have yielded results which would indicate that not only periplanone-B, but also periplanone-A could be a genuine pheromone. With single cell recording techniques he demonstrated the presence of many olfactory hairs on the antennae of Periplaneta americana that were very sensitive to periplanone-A, whereas others were sensitive for periplanone-B (41). 

From 1976 to 1978, tremendous efforts were spent on the isolation of a major component (in a pure form) of the sex pheromone of the female cockroach, Periplaneta americana. The potency of the compound isolated, periplanone B, was truly amazing (threshold limits of 10 pg). It was considered to be a promising agent to control this pest. However, only trace amounts were isolated from natural sources (a total of 0.2 mg isolated from 75 000 specimens). Even the use of modern methods of instrumental analysis did not lead to the elucidation of its complete structure. With the help of these methods it was possible only to ascertain the basic structural features, as shown in formula 59a (Scheme 1.16). The problem of its stereochemistry remained unanswered. This most difficult part of the problem was finally solved only after a total synthesis of three of four possible geometrical isomers of periplanone Comparison of the spectral parameters of synthetic samples with those of the natural periplanone B determined the stereochemistry as shown in structure 59b. A minor component of the same pheromone, periplanone A, was available in even... 

The female-produced sex pheromone of the American cockroach (Periplaneta americana) consists of the four components, periplanones-A, B, C and D, periplanone-B being the major component (Figure 4.17).37 Periplanones-A and B were isolated in 1974 by Persoons in the Netherlands. The structure of periplanone-B was proposed by him in 1976, confirmed by its synthesis, and its absolute configuration was determined, as depicted in Figure 4.17. We achieved two different enantioselective syntheses of the naturally occurring (- )-periplanone-B, 38,39... 

There are two main ways of gaining specificity in pheromone signals. One is by the evolution of a large unique molecule. Peptide pheromones, using the 20 coded amino acids available in eukaryotic systems, offer an extraordinary variety of unique sequences with a five amino-acid polypeptide there are 20 ( 3.2 million) (Browne et al., 1998). For example, two related species of the newt Cynops have species-specific decapeptide pheromones which differ by just two amino acids (Yamamoto et al., 2000). Among insects, a very few species use a unique complex molecule as a single component pheromone for example, periplanone-B is the sex pheromone of the American cockroach (Periplaneta americana) (Roelofe, 1995). 

Periplanones A-D act, in contrast to long-range pheromones, as close proximity sex-excitants They arc found in the alimentary tract and excreta of the female American cockroach Periplaneta americana, and cause the males to run and to perform the courtship display. Periplanones A and B, occurring in a ratio of 10 1, arc 100 times more active than C and D. 

Periplanone B is the most active sex pheromone found in the alimentary tract and excreta of the American cockroach Periplaneta americana. An elegant total synthesis of this germacrane sesquiterpene was achieved by SCHREIBER and SANTINI Cyclodecatrienone 1 is an obvious precursor. One of the oxirane rings arises from epoxidation of the enone CC double bond, the other from [2-1-1]-cycloaddition of a carbene to the carbonyl bond of the enone. Oxidation of the methylene group introduces the additional carbonyl double bond. The CC double bond of the enone results from an elimination of HX in the a-X-substituted cyclodecadienone 2, which, on its part, is feasible by substitution of cyclodecadienone 3. An electrocyclic opening of the cyclobutene ring in 4 provides the 1,3-diene substructure in 3. 

Fig. 4.4 Upwind orientation by the male cockroach, Periplaneta americana, in a plume of synthetic female sex pheromone, periplanone B. Plume widths at 1.0 m from the pheromone source (a and b) 8 cm (c and d) 28 cm. Wind direction is from left to right in the diagram wind speed is 22 cm s . S, position of the pheromone source (Tobin, 1981).

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