Ants, Pharaoh

A trail pheromone of the Pharaoh ant was identified as 3-butyl-5-methylindolizidine of the stereochemistry given in (219) (75JHC289). Slaframine (220) is a metabolite isolated from Rhizoctonia leguminicola responsible for producing excessive salivation in cattle. A stereoselective synthesis was reported (73JOC3848). Swainsonine (221), a potent inhibitor of a-mannosidase, has been isolated from Swainsona caneszens. The stereochemistry was derived from the NMR spectrum (79AJC2257). 

Recently, a glandular secretion of the Pharaoh ant has been isolated and identified as 3-butyl-5-methylindolizidine.257 Oliver and Sonnet have successfully synthesized its four stereoisomers.258,259 Routes are shown in Scheme 27.258... 

This reaction was used to synthesize faranal (1), the trail pheromone of the pharaoh ant.2... 

The seco-phenanthroindolizidine alkaloid septicine has been synthesized by a nitrone route. A cycloaddition of 1-pyrroline 1-oxide with 2,3-bis-(3,4-dimethoxyphenyl)butadiene gives two stereoisomeric isoxazolidines, one of which is converted into ( ) septicine.10 ( )-Tylophorine and 5-coniceine have been prepared by a new route that makes use of an intramolecular imino-Diels-Alder reaction.11 A stereoselective synthesis of 3,5-dialkyl-indolizidines has been applied to the synthesis of a stereoisomer of the trail pheromone of the Pharaoh ant and to a stereoisomer of gephyrotoxin 223.12 A stereoselective total synthesis of ( )-perhydrogephyrotoxin (21)13 and a simple synthesis of ( )-gephyran14 have been reported. 

Carbon-13 n.m.r. assignments have been reported for a number of isomeric 3-butyl-5-methyloctahydroindolizines that were synthesized in studies of the trial pheromone of the Pharaoh ant, and for some closely related indolizidines. This work includes a detailed discussion of the preferred conformations of these compounds.15 Securinegine, a minor alkaloid from Securinega suffruticosa Rehd., is isomeric with securinine, and the structure (22) has been proposed.16... 

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... 

Pyrroline is a desirable starting material for alkylation of heterocycles. 1-(Methoxycarbonyl)-3-pyrroline2 has been used to prepare 2,5-dialkylated pyrrolines,3 which resulted in the synthesis of the Pharaoh ant trail pheromone43 and gephyrotoxin 2 2 3.4b Alkylation of 3-pyrrolines has also led to the synthesis of 12-azaprostaglandins.5 The submitters have used a formamidine derived from 3-pyrroline to provide access to 2-substituted pyrrolines and pyrrolidines,6 which has led to the synthesis of the unnatural (+)-anisomycin.7... 

Urethanes analogous to the amides of the previous section undergo similar deprotonation followed by alkylation and condoisation reactions. For example, 2,4,6-tri-r-butylphenol may be converted into the corresponding urethane which can be further functionalized (equation 32). N-Carbomethoxy-3-pyrroline has been convoted into both the trail pheromone for the Pharaoh ant and gq)hyrotoxin 223 by using regiospecific alkylations (Scheme 3). ° Similar tqjproaches were used in the preparation of the natural product supinidine. Piperidines also have been alkylated via the r-BOC-protected amines. ... 

Anodic oxidation of amides and carbamates on the other hand are far more useful than those of amines. Scheme 46 shows the synthesis of a pharaoh ant trail pheromone in which the anodic oxidation of 2-pyrrolidone is an important step [270]. 

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... 

A trail substance of the Pharaoh ant, Monomorium pharaonis (L), has been identified as a 3-butyl-5-methyloctahydroindolizine of unknown stereochemistry. The four isomers (6a—d) have now been prepared by methods which allow the stereochemistry at C-3, C-5, and C-9 to be assigned. Reaction of 2,6-lutidine (7) with n-butyl-lithium and 1,2-epoxyhexane gave the alcohol (8), which on treatment... 

Reduetive alkylation of heteroaromatic rings is possible using catalytic hydrogenation. 34 Cyclization of the substituted pyridine 442 was induced by treatment with triphenylphosphine bromine, and generated pyridinium salt 443. Isolation of 443 by Sonnet was followed by hydrogenation with platinum, generating the trail pheromone of the Pharaoh ant (3-butyl-5-methyloctahydroindolizine, 444). 35... 

This reaction was adapted to the synthesis of the pharaoh ant pheromone monomorine. 

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. 

Indolizidine alkaloids are produced by the Pharaoh ant, Monomorium pharaonis. This tropical ant is now a common... 

Klotz, J.H., K.M. Vail, D.R Williams, Liquid boric acid bait for control of structural infestations of pharaoh ants, J. Econ. EntomoL, 90(2), 523-526, 1997. 

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