Biosynthesis of a defensive insect alkaloid: epilachnene from oleic acid and serine.

Attygalle, Athula B.; Blankespoor, Curtis L.; Eisner, Thomas; Meinwald, Jerrold

doi:10.1073/pnas.91.26.12790

Cited by 31 publications

(20 citation statements)

References 5 publications

(5 reference statements)

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“…The samples obtained by these procedures were each dissolved in 0.6 ml of benzene-d 6 and subjected directly to NMR analysis. Subsequently, the NMR solvent was removed, and the samples were analyzed by HPLC and GC.…”

Section: Methodsmentioning

confidence: 99%

“…4 and 5). Studies on the biosynthesis of the azamacrolides showed that epilachnene (1) can be produced from oleic acid and serine (6). The composition of the pupal secretion of another species of Epilachna (E. borealis, the squash beetle), is far more complex, in that it consists of a combinatorial library containing over a hundred macrocyclic polyamines, the polyazamacrolides (PAMLs; for example, 3-5; Fig.…”

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confidence: 99%

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Polyazamacrolides from ladybird beetles: Ring-size selective oligomerization

Schroeder

Smedley

Gibbons

et al. 1998

Proc. Natl. Acad. Sci. U.S.A.

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The pupal defensive secretion of the 24-pointed ladybird beetle, Subcoccinella vigintiquatuorpunctata, consists of a mixture of macrocyclic polyamines, dominated by the three dimeric, 30-membered macrocycles 11-13, derived from the two building blocks 11-(2-hydoxyethylamino)-5-tetradecenoic acid (9) and 11-(2-hydoxyethylamino)-5,8-tetradecadienoic acid (10). Smaller amounts of the four possible cyclic trimers of 9 and 10 were also detected, corresponding to 45-membered macrocycles. Structural assignments were based on NMR-spectroscopic investigations and HPLC-MS analyses. In addition, the all-S absolute configuration of the S. vigintiquatuorpunctata macrocycles was determined by comparison of derivatives of the natural material with enantiomerically pure synthetic samples. Comparing this alkaloid mixture with that of the pupal defensive secretion in related ladybird beetle species indicates that the degree of oligomerization of the 2-hydroxyethylamino carboxylic acid building blocks can be carefully controlled by the insects.

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Polyazamacrolides from ladybird beetles: Ring-size selective oligomerization

Schroeder

Smedley

Gibbons

et al. 1998

Proc. Natl. Acad. Sci. U.S.A.

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“…The compounds detected show the profile of living Cucujus because the sampling was performed on the beetles in a non-invasive way. In these insects, among the molecules detected we found several fatty acids, which are reported and identified as defensive substances in other arthropods (Attygalle et al 1994). In particular, oleic acid is reported to play a defensive or repellent role in many other insects.…”

Section: Discussionmentioning

confidence: 82%

“…Fatty acids are involved in some important biochemical pathways of insects; indeed, they play a major role in several physiological functions and are used also as pheromones or defensive substances. For example, toxic alkaloids derived from the unsaturated fatty acid, and in particular oleic acid (Attygalle et al 1994), were identified in coccinellid beetles. Oleic acid (C18H34O2) has been detected only in a few taxa, such as Formicidae, Termites and Chrysomelidae (Wilson et al 1958).…”

Section: Discussionmentioning

confidence: 99%

Beetles “in red”: are the endangered flat bark beetles Cucujus cinnaberinus and C. haematodes chemically protected? (Coleoptera: Cucujidae)

Bonacci

Mazzei

Naccarato

et al. 2018

The European Zoological Journal

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Two native species of the genus Cucujus show a wide geographic distribution in Europe, Cucujus cinnaberinus (Scopoli, 1763) and C. haematodes Erichson, 1845. Although data on the distribution and ecology of these rare and endangered species are increasing, there are few reports on their biology and behaviour, and some aspects of their feeding ecology remain problematic. Our aim was to study, for the first time, the cuticular chemical profiles of these two beetles to (i) investigate the presence of chemicals potentially involved in defence by pathogens and (ii) lay the foundation for understanding the role of their bright red colour. The analysis of the cuticular profile was performed in-vivo by solid phase microextraction coupled with gas chromatography-mass spectrometry. In the cuticular profiles of the two species we identified 24 compounds belonging to different classes of molecules, i.e. hydrocarbons, aldehydes, esters, n-alkyl morpholines, and a high number of organic acids. Qualitative differences in terms of both signal intensity and detected compounds were found between the two species. As reported in other insects, the remarkable array of avoidance substances suggests a strict relationship with the bright red colour of the adults, which probably acts as an aposematic or warning signal. European Cucujus species are probably well protected against enemies because some identified chemicals, particularly fatty acids, are related to an antipredatory strategy to fight off predators that use their sense of smell to locate their prey. Other substances found on the cuticular layer of these beetles are probably involved in an antimicrobial and antifungal function, as demonstrated in other insects living in habitats that host many pathogens.

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“…varivestis to determine the possible sources of both the 14-carbon straight chain and the ethanolamine moieties of epilachnene (28 To confirm this structure, we devised a synthetic route to CNS 2103 which has the virtue of being easily modified to give access to a variety of unnatural analogs of the spider neurotoxin as well (31). It is of particular interest that polyamines closely related to CNS 2103 have been found not only in other spider species (29) but also in the venom of the solitary digger wasp Philanthus triangulum (32).…”

Section: Desoxycorticosteronementioning

confidence: 99%

The chemistry of phyletic dominance.

Meinwald

Eisner

1995

Proc. Natl. Acad. Sci. U.S.A.

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Studies of arthropod defensive chemistry continue to bring to light novel structures and unanticipated biosynthetic capabilities. Insect alkaloids, such as the heptacyclic acetogenin chilocorine and the azamacrolides, exemplify both of these aspects of arthropod chemistry. Spider venoms are proving to be rich sources of neuroactive components of potential medical interest. The venom of a fishing spider, Dolomedes okefinokensis, has yielded a polyamine which reversibly blocks L-and R-type voltage-sensitive calcium channels. Most recently, we have characterized, from the funnel-web spider Hololena curta, a sulfated nucleoside glycoside which serves as a reversible blocker of glutamatesensitive calcium channels. The ability to synthesize or acquire an extremely diverse array of compounds for defense, offense, and communication appears to have contributed significantly to the dominant position that insects and other arthropods have attained.

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Biosynthesis of a defensive insect alkaloid: epilachnene from oleic acid and serine.

Abstract: The biosynthesis of the azamacrolide epilachnene by the coccinellid beetle Epilachna varivestis has been studied with 2H-labeled oleic acid, 2H-labeled L-serine, and

Cited by 31 publications

References 5 publications

Polyazamacrolides from ladybird beetles: Ring-size selective oligomerization

Polyazamacrolides from ladybird beetles: Ring-size selective oligomerization

Beetles “in red”: are the endangered flat bark beetles Cucujus cinnaberinus and C. haematodes chemically protected? (Coleoptera: Cucujidae)

The chemistry of phyletic dominance.

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