Biosynthesis of the Solenopsins, Venom Alkaloids of the Fire Ants

Leclercq, Sabine; Braekman, Jean Claude; Daloze, Désiré; Pasteels, Jacques; Meer, Robert K. Van der

doi:10.1007/s001140050276

Cited by 12 publications

(19 citation statements)

References 10 publications

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“…In S. invicta , it appears that both hydrocarbons and piperidines may play roles in providing information relevant to regulation of colony queen number, as described above. Like hydrocarbons, piperidines are derived from acetate (Leclercq et al, 1996), raising the possibility that similar metabolic processes regulate the synthesis of hydrocarbon chains and piperidines.…”

Section: Discussionmentioning

confidence: 99%

Venom Alkaloid and Cuticular Hydrocarbon Profiles Are Associated with Social Organization, Queen Fertility Status, and Queen Genotype in the Fire Ant Solenopsis invicta

et al. 2011

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Queens in social insect colonies advertise their presence in the colony to: a) attract workers’ attention and care; b) gain acceptance by workers as replacement or supplemental reproductives; c) prevent reproductive development in nestmates. We analyzed the chemical content of whole body surface extracts of adult queens of different developmental and reproductive stages, and of adult workers from monogyne (single colony queen) and polygyne (multiple colony queens) forms of the fire ant Solenopsis invicta. We found that the composition of the most abundant components, venom alkaloids, differed between queens and workers, as well as between reproductive and non-reproductive queens. Additionally, workers of the two forms could be distinguished by alkaloid composition. Finally, sexually mature, non-reproductive queens from polygyne colonies differed in their proportions of cis-piperidine alkaloids, depending on their Gp-9 genotype, although the difference disappeared once they became functional reproductives. Among the unsaturated cuticular hydrocarbons characteristic of queens, there were differences in amounts of alkenes/alkadienes between non-reproductive polygyne queens of different Gp-9 genotypes, between non-reproductive and reproductive queens, and between polygyne and monogyne reproductive queens, with the amounts increasing at a relatively higher rate through reproductive ontogeny in queens bearing the Gp-9 b allele. Given that the genotype-specific piperidine differences reflect differences in rates of reproductive maturation between queens, we speculate that these abundant and unique compounds have been co-opted to serve in fertility signaling, while the cuticular hydrocarbons now play a complementary role in regulation of social organization by signaling queen Gp-9 genotype.

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Section: Discussionmentioning

confidence: 99%

Venom Alkaloid and Cuticular Hydrocarbon Profiles Are Associated with Social Organization, Queen Fertility Status, and Queen Genotype in the Fire Ant Solenopsis invicta

et al. 2011

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“…Therefore, we assume that the alkaloidal components in fire ant queens have the same Fig. As didehydropiperidines have been proposed to function as precursors for the syntheses of fire ant alkaloids [16] [21], the absolute configuration of didehydropiperidines can be inferred to (2R)-Me for 1,2-didehydropiperidine 4 and (6R)-C 11 H 23 for 1,6-didehydropiperidine (5). Mass spectra of new alkaloids identified from alate queens configuration as those in fire ant workers.…”

Section: 'mentioning

confidence: 99%

Similarity in Venom Alkaloid Chemistry of Alate Queens of Imported Fire Ants: Implication for Hybridization between Solenopsis richteri and S. invicta in the Southern United States

Chen

et al. 2012

Chemistry & Biodiversity

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Both cis- and trans-2-methyl-6-undecylpiperidines, MC11P, have been previously reported as the major components of the venom of alate queens of the imported fire ants, Solenopsis richteri (black) and S. invicta (red). To identify the minor components of venom alkaloids from alate queens and compare the venom alkaloid chemistry of alate queen of their hybrid (S. richteri×S. invicta) with that of the two parental fire ant species (S. richteri and S. invicta), silica-gel short-column chromatography was utilized for separating cis-stereoisomers of venom alkaloids from trans-stereoisomers. GC/MS Analyses of venom-alkaloid chemistry of alate queens demonstrated that fewer alkaloid peaks were detected in the chromatograms of the alate queens compared to those of workers. Three new compounds, 7, 12, and 13, were detected as minor components in the venom of alate queens of all three fire ant species. Alate queens of hybrid fire ants showed cis- and trans-alkaloid patterns similar to those of the parental species. Similarity in venom-alkaloid chemistry of alate queens of S. richteri and S. invicta, and their hybrid may indicate their reproductive compatibility in the hybrid zone in southern United States, where all three species occur sympatrically.

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“…In nature, the asymmetric reduction of imines to the corresponding amines is catalysed by imine reductases (IREDs). These enzymes are NADPH‐dependent oxidoreductases and are related to several biosynthetic pathways including the one affording ant venom alkaloids ,. Recently, IREDs have been extensively applied to reduce a wide range of prochiral cyclic imines generating chiral monosubstituted piperidines and pyrrolidines, often with high conversion and enantiomeric excess…”

Section: Resultsmentioning

confidence: 99%

“…The proposed biosynthetic route to solenopsins, the most abundant alkaloid class found in the Solenopsis ant venom, inspired a multi‐enzymatic cascade process to the synthesis of 2,5‐disubstututed pyrrolidines (Scheme ). This cascade involves the transamination of the less hindered carbonyl group of a diketone ( 1 ), catalysed by a stereoselective transaminase ( R ‐ or S ‐TA), producing the enantiopure aminoketone 2 , which spontaneously cyclizes affording the corresponding imine 3 .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 2,5‐Disubstituted Pyrrolidine Alkaloids via A One‐Pot Cascade Using Transaminase and Reductive Aminase Biocatalysts

et al. 2018

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A multi‐enzymatic cascade process involving transaminases (TAs) and reductive aminases (RedAms) to produce enantiomerically pure 2,5‐disubstituted pyrrolidine alkaloids from their respective 1,4‐diketones is reported. Several TAs were screened and the best results for diketone monoamination were obtained with an R‐selective TA from Mycobacterium chlorophenicum and with an S‐selective TA from Bacillus megaterium. Pyrroline reduction was best performed by a reductive aminase from Ajellomyces dermatitidis (AdRedAm). Finally, a biocatalytic one‐pot cascade was implemented using the aforementioned enzymes and a variety of 2‐methyl‐5‐alkylpyrrolidines were produced with high (>99 %) conversion, diastereomeric and enantiomeric excess values.

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Biosynthesis of the Solenopsins, Venom Alkaloids of the Fire Ants

Cited by 12 publications

References 10 publications

Venom Alkaloid and Cuticular Hydrocarbon Profiles Are Associated with Social Organization, Queen Fertility Status, and Queen Genotype in the Fire Ant Solenopsis invicta

Venom Alkaloid and Cuticular Hydrocarbon Profiles Are Associated with Social Organization, Queen Fertility Status, and Queen Genotype in the Fire Ant Solenopsis invicta

Similarity in Venom Alkaloid Chemistry of Alate Queens of Imported Fire Ants: Implication for Hybridization between Solenopsis richteri and S. invicta in the Southern United States

Synthesis of 2,5‐Disubstituted Pyrrolidine Alkaloids via A One‐Pot Cascade Using Transaminase and Reductive Aminase Biocatalysts

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