Pharaoh’s ant

An alternative strategy for (1) would have been to reconnect both substituents into a ring to ensure their ais arrangement. This strategy was used in syntheses of the antibiotic methylenomycin (4) and the trail pheromone of pharaoh s ant, faranal (5). 

Mori reported an improved synthesis of (3S,4P,6 ,10Z)-faranal (37), the trail pheromone of the Pharaoh s ant (Monomorium pharaonis) [84]. As summarized in Scheme 55, the key-reaction was the coupling of iododiene A with iodide E. The geometrically pure A was prepared by the zirconocene-mediated carbo-alumination reaction, and E was prepared from B by the asymmetric cleavage of its epoxy ring to give C (77% ee), which could be purified via its crystalline 3,5-dinitrobenzoate D. 

The queen is usually reproductively dominant within the colony and uses chemical cues as both primer and releaser pheromones to suppress the production or fecundity of other sexuals, inhibit reproduction by worker castes, modulate reproductive behaviors (e.g., inhibit swarming and orient swarms), attract males, regulate worker tasks and worker ontogeny, and produce host repellents in slave-making species. Considering the importance of queen semiochemicals in social hymenoptera, few queen pheromones have been chemically identified. The queens of most social hymenopteran colonies are attractive to workers, allowing them to be properly tended as well as to facilitate the dissemination of other pheromone cues. However, the retinue pheromone has been chemically identified in very few species. In the 1980s, queen pheromone components were identified in the fire ant, Solenopsis invicta [91,92], and in the Pharaoh s ant, Monomoriumpharaonis [93]. 

Workers of pharaoh s ant, Monomorium pharaonis, utilize their poison gland secretion as an effective repellent in the same way as that of thief ants, Solenopsis (Diplorhoptrum) species, in order to steal brood from the nests of other... 

We end with an example that includes methods from this chapter as well as some revision and a reminder of stereochemistry. Monomorine I 71 is the trail pheromone of Pharaoh s ant (Monomorium pharaonis). These ants are pests in hospitals as they spread infections and they follow a trail of monomorine as they go about their evil work. Synthetic monomorine might be... 

In a review of current work on the trail pheromone of the Pharaoh s ant, Monomorium pharaonis, it is reported that natural monomorine III is the all-cw-... 

A few years ago the complete structure of periplanone-B, apart from its stereochemistry, was elucidated and published by our research team (32,33,34) with Persoons as the principal investigator, who included this work in his doctoral thesis (35), and shared the Royal Dutch Shell Prize for 1978 with Ritter for this work and the structure elucidation of faranal, the trail pheromone of the Pharaoh s ant, Monomorium pharaonis (36,37). 

S,4R,6E,10Z)- F- aranal C l 10 Pharaoh s ant Monomorium pharaonis) T Zirconoceire- mediated carboaluminalion reaction [167]... 

This is the most common relationship, and the majority (about 70%) of the chiral pheromones belongs to this category. Only the (lR,5S,7R)-isomer of exo-brevicomin (entry 41) is bioactive [207]. (3S,4R)-Faranal (entry 19) is the bioactive enantiomer of the trail following pheromone of the pharaoh s ant [208]. 

In 1977, Ritter and coworkers in the Netherlands isolated and identified faranal (95, Figure 4.46), the trail-following pheromone of the workers of the Pharaoh s ant (.Monomorium pharaonis). The detection threshold of 95 is about 1 pg/cm of a trail. This remarkable bioactivity of 95 attracted the attention of... 

The same methodology is applied in the enantioselective synthesis of iodo ether 23, a key precursor of ( + )-faranal (24) (a trail pheromone of the Pharaoh s ant)969. 

A high degree of chiral transmission is observed in the synthesis of iodo acetal 19, a key intermediate in the total synthesis of ( + )-faranal (a trail pheromone of the Pharaoh s ant). The [2,3] Wittig process ot 16 followed by cis hydrogenation gives oxy-Cope substrate 17 with 100% E and Z and >99% threo. The oxy-Cope process of 17 affords en7//ro-aldehyde 18 as a single product with 91 % ee966. 

S.4R.6L.10Z)- Karanal nK Pharaoh s ant (Monoworium pharaonis) r Zirconoeene-mcdiaicd carboa 1 um ination reaction [I67 ... 

Pheromones.—Further use has been made of Bestmann s unitized construction principle to synthesize a variety of 1,5- and 1,6-alkadiene pheromones. Standard Wittig methods have been used to synthesize (3Z,6Z,9Z)-1,3,6,9-nonadecatetraene (142) (Scheme 19) (now identified as a sex pheromone of the winter moth O. brumata), sex attractants (143) of Lasiocampidae species, and the trail pheromone (144) of Pharaoh s ant. A variety of 2,4-dienoic ester insect juvenile hormone analogues (145) with terminal cyclohexene, cyclohexane, or pinene rings have been prepared by phosphonate olefination. The queen... 

Another natural product, (+ )-faranal (27), a trail pheromone of the Pharaoh s ant, has also been synthesized starting with 2 (see Scheme 3) [11].The crucial transformation in the sequence is a [2,3] Wittig rearrangement of 24 which, after cw-hydrogenation, gives diene 25 in > 96% ee. This intermediate, when treated with potassium hydride, undergoes an anionic oxy-Cope rearrangement to afford the erythro aldehyde 26 in 91% ee. 

The indolizidine alkaloid (+ )-monomorine I (373), isolated from Pharaoh s ant Mono-morium pharaonis, is the first example of an indolizidine alkaloid found in the animal kingdom. One enantioselective total synthesis of 373 exploits an asymmetric cycloaddition of nitrone 370 to the chiral allylic ether 369, which is prepared from 349. The conversion of 349 to a tosylate followed by treatment with -propylmagnesium bromide in the presence of... 

OZ)-3,4,7,11 -tetramethyltrideca-6,10-dienal (faranal), the trail pheromone of Pharaoh s ant, Monomorium pharaonis, In one approach, racemic (3S,47 /3/ ,45) faranal (54) was synthesised by a route in which stereospecific formation of a trisubstituted double-bond and a substituted vinyl iodide was controlled by addition of alkyl-copper complexes to terminal acetylenic derivatives. The relative configuration of the methyl groups at C-3 and C-4 was established by the use of c fs-4,5-dimethyl cycl ohexene as an important intermediate (Scheme 8). ... 

Ritter, F. J., Bruggeman-Rotgans, I. E. M., Verweil, P. E. J., Persoons, C. J. and Tal-man, E. (1977) Trail pheromones of the Pharaoh s ant, Monomorium pharaonis isolation and identification of faranal, a terpenoid related to juvenile hormone II. Tetrahedron Letters, 2617-18. 

Faranal (Figure 6.25) is the trail pheromone of Pharaoh s ant Mono-morium pharaonis, a tropical species that has become a pest inside warm buildings in temperate climates. It contains two homomevalonate... 

Figure 9.10 More complex alkaloids from ants The indolizidines where R is butyl, hexyl and 3-hexenyl have been known from the venom o/Monomorium pharaonis, pharaoh s ant, for some time. The 2-heptyl-8-methyl-pyrrolizidine is from a Soienopsis ant. The keto-indolizidine is from an African Myrmicaria ant. There are eight of the tetraponerines from Tetraponera species from New Guinea...

---