Selectivity, pheromones

Plettner E., Slessor K. N., Winston M. L. and Oliver J. E. (1996) Caste-selective pheromone biosynthesis in honeybees. Science 271, 1851-1853. 

The Initial phase of the development was the determination of the relative solubility of the selected pheromone, ZZ and ZE-7, 11-hexadecadlenyl acetate (Gossyplure, 1 1 ratio). In a suitable polymer matrix. Four different water-soluble or water-reducible resins were Initially Investigated a water-soluble acrylic mixture, two latex emulsions and a natural rubber colloid. Intrln- sic solubility was determined by making resln/pheromone solutions of varying concentrations and measuring the rate of pheromone diffusion from dried films. In this manner, we were able to determine the most suitable base polymer from which to begin. 

Table A gives an up-to-date compilation of selected pheromones in the insects, its species, type of pheromone and synthetic key-step. The class of pheromones most widely explored are the sex pheromones in insects. In most cases they are produced by a female to attract a male of the same species. Today, the pheromones of more than 400 species and a...

Tabic A. Synthesis of selected pheromones including iis kevslcp. 

When allylic compounds are treated with Pd(0) catalyst in the absence of any nucleophile, 1,4-elimination is a sole reaction path, as shown by 492, and conjugated dienes are formed as a mixture of E and Z isomers[329]. From terminal allylic compounds, terminal conjugated dienes are formed. The reaction has been applied to the syntheses of a pheromone, 12-acetoxy-1,3-dode-cadiene (493)[330], ambergris fragrance[331], and aklavinone[332]. Selective elimination of the acetate of the cyanohydrin 494 derived from 2-nonenal is a key reaction for the formation of the 1,3-diene unit in pellitorine (495)[333], Facile aromatization occurs by bis-elimination of the l,4-diacetoxy-2-cyclohex-ene 496[334],... 

Two illustrations that show the power of this reaction for the preparation of strained cycloalkenes are the contractions of 102 to the propellane 103 , an application that has been reviewed , and of 104 to the bicyclo[2.1.1]hexene 105 . The utility of the Ramberg-Backlund rearrangement in the preparation of various natural products such as steroids , terpenoids and pheromones has been demonstrated. In addition to the synthetic applications mentioned in the previous subsection, several selected examples taken from the recent literature are given in equations 66-69. These examples further demonstrate the potential of this method for alkene synthesis in general. 

An enantio-selective enzymatic hydrolysis of meso( )-2,5-diacetoxy-3-hexene gives (+)-( )-(25 ,5/ )-5-acetoxy-3-hexen-2-ol in 77% yield (92% ee).97 The monoacetate with its two allylic groups offers possibilities for stereo-controlled introduction of nucleophiles via Pd(0) catalysis. Synthesis of both enantiomers of the Carpenter bee pheromone based on this strategy is presented in Scheme 5.14.98... 

A strategy to access lactones via enzymatic hydrolysis of y- and /3-hydroxy aliphatic nitriles to their corresponding acids with subsequent internal esterification was applied using commercially available enzymes from BioCatalytics Inc. A number of y- and /3-hydroxy aliphatic nitrile substrates (Table 8.11) were evaluated, with the greatest selectivity observed with y-hydroxy nonanitrile, which was converted by nitrilase NIT1003 to the precursor of the rice weevil pheromone in 30% yield, 88% ee with an enatiomeric ratio of = 23 [90],... 

Scheme 41 summarizes Couladouros s synthesis of the oviposition attractant pheromone of the Southern house mosquito (Culexpipiensfatigans)y (5R,6S)-6-acetoxy-5-hexadecanolide (28) [66]. The key-steps are (i) -selective Schlosser olefination (A B), asymmetric dihydroxylation (B C), and lactonization of carbonate C to the desired 6-lactone with inversion at C-5. 

Different from the use of ordinal insecticides, this disruption method has high target selectivity and, as would be desired, ensures the survival of natural enemies. The sex pheromone, which shows no toxicity to mammals, is an ideal insect-behavior regulator (IBR). Table 8 shows the application areas of main mating disruptants for lepidopteran insects. In addition to the use of the synthetic pheromone of P. gossypiella in large cotton fields, many disruptants are... 

As with the other insects studied that utilize hydrocarbon sex pheromones, once Z9-23 H is produced by oenocyte cells it is released into the hemolymph. Lipophorin is the transport protein that will move the hydrocarbon to cuticu-lar tissue [21]. It was found that about 24 h were required once Z9-23 H was induced to actual deposition on the cuticular surface [237]. As is the case with other insects selective partitioning of the sex pheromone was observed with relatively larger proportions of Z9-23 H being found on the cuticular surface than in other tissues [21]. 

Parasitic hymenoptera hold promise in integrated pest management schemes, because they parasitize many economically important insect pests in a species-and stage-selective manner. The pheromones and kairomones of the parasitic hymenoptera have been studied for a long time, and there are many examples where there is evidence of chemical mediation of parasitoid behavior. This review emphasizes work done since the last major reviews [11, 12, 42] and, where it is available, on the primary bioassay-guided chemical identification of the semiochemical (Fig. 2 and Tables 3 and 4). 

Another elegant use of nonadienoate is the synthesis of a pheromone called brevicomin (148) (132). The ester was converted to 1,6-nonadiene (149). The terminal double bond was selectively converted to glycol via epoxide. The oxidation with PdCI2 produced brevicomin directly by intramolecular oxidative acetal formation. 

Industrial synthesis of vitamin A (Hoffman-La-Roche) goes through partial hydrogenation of an enyne (equation 161)277. A number of syntheses of pheromones, where the reduction of an enyne to a diene is the key step, have been devised. A few selected examples are given in Table 29278. During the total synthesis of endiandric acids, Nico-laou employed hydrogenation of a polyenyne intermediate with a Lindlar catalyst to generate an intermediate which underwent symmetry-allowed cyclizations to result in the natural product (equation 162)279. 

Loconto, J. et al. Functional expression of murine V2R pheromone receptors involves selective association with the M10 and Ml families of MHC class lb molecules. Cell 112 607-618, 2003. 

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