Monomorium pharaonis pheromone

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. 

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-... 

Certain 2,5-dialkyl-pyrrolidines, which are trail pheromones of the pharaoh ant (Monomorium pharaonis L.), have been synthesized by application of the Hofmann-Loffler reaction to 5-aminotridecane and 7-aminopentadecane. The same type of compound results from Seebach alkylation of TV-nitrosopyrrolidines.4... 

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). 

All the currently known indolizidine and quinolizidine alkaloids isolated from ants are illustrated in Fig. 6. (+ )-Monomorine I (427), the well-studied trail pheromone constituent of the Pharaoh ant Monomorium pharaonis), and the analogs 428-431 were described in the earlier volumes in this series. These five compounds are 3,5-disubstituted indolizidines bearing short saturated or mono-unsaturated hydrocarbon chains. The relative stereochemistry in monomorine VI (430) still remains unknown, while that of 431 was atypical for the class at the time of its isolation 380). The structural resemblance of fiiis group of alkaloids to the... 

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... 

From the above survey of results the synthetic potential of the oxazinolactam intermediate 46 in hand, we envisaged to synthesize monomorine I (62) which constitutes of an extension of the methodology based on intramolecular nitroso Diels-Alder cycloaddition. The relative stereochemistry of this substance, isolated as one of the trail pheromones from Pharaoh ants (Monomorium pharaonis L.) (ref. 19), has been determined its relative stereochemistry by nonstereoselective synthesis (ref. 20). More recently, a stereospecific synthesis of racemic 62 (ref. 21) and a chiral synthesis of the (-)-enantiomer of natural 62 (ref. 22) were reported. 

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). ... 

Fig. 15.10 Trail pheromones identified from myrmicine ants, indicating the diversity of structures encountered. ( l) Atta texana (Tumlinson et al., 1972) andcephalotes (Riley et al.y 1974b) (b) A. sexdens rubropilosa (Cross et aL, 1979) and Myrmica spp. (Ever-shed et al., 1981) (c) Lasius fuliginosus (Huwyler et al., 1975) (d) Monomorium pharaonis (Ritter et al., 1977) (e) Solenopsis invicta (Williams et a/., 1981 Vandermeer etal., 1981).

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. 

The octahydroindolizine trail pheromone (412) of the Pharaoh ant (Monomorium pharaonis) was first prepared by Ritter et al. (181) as a mixture of stereoisomers, beginning with a termolecular condensation (Scheme 74). Oliver and Sonnet (182) then unambiguously synthesized the four stereoisomers from 2,6-lutidine (413) (Scheme 75) and 2-butyl-pyrrole (418) (Scheme 76). 

Ritter, F., I. E. Rotgans, E. Talman, P. E. Verwiel, and F. Stein 5-Methyl-3-butyl-octahydroindolizine, a novel type of pheromone attractive to Pharaohs ants (Monomorium pharaonis (L)). Experientia 29, 530—531 (1973). 

The synthesis of faranal, the trail pheromone of the common ant Monomorium pharaonis, was recently reported by Minnaard, Feringa, and coworkers [4]. Hence, CM of 5 with ethyl thioacrylate furnished the unsaturated thioester 6 in good yield along with 5% of the homodimer of 5 (Scheme 10.2). The second stereocenter was installed by an enantioselective conjugate addition, which led to 7 in both high yield and high selectivity. 

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