Iridoid biosynthesis in staphylinid rove beetles (Coleoptera: Staphylinidae, Philonthinae)

Weibel, Douglas B.; Oldham, Neil J.; Feld, Birte K.; Glombitza, Gereon J.; Dettner, Konrad; Boland, Wilhelm

doi:10.1016/s0965-1748(00)00163-6

Cited by 24 publications

(19 citation statements)

References 22 publications

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“…[6] Consistent with the previously studied stereochemical course of iridoid biosynthesis, [7,12] loss of a single deuterium atom from C(4) of the precursor was observed in 1 produced by feeding larvae of P. cochleariae (Scheme 3), H. marginella and P. vulgatissima. The same observation was made for 2, generated from [ 2 H 5 ]-9 by the larvae of P. versicolora, P. laticollis, L. aenea, P. vulgatissima and P. phellandrii, as well as for plagiolactone produced by P. versicolora, L. aenea and H. marginella, and for 3 produced by G. cyanea.…”

Section: Resultssupporting

confidence: 83%

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Beetles Do It Differently: Two Stereodivergent Cyclisation Modes in Iridoid‐Producing Leaf‐Beetle Larvae

et al. 2013

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Larvae of the Chrysomelina species Phaedon cochleariae, Hydrothassa marginella, Phratora vulgatissima, Gastrophysa viridula, Gastrophysa atrocyanea, Gastrophysa cyanea and Gastrophysa polygoni produce the iridoid chrysomelidial (1) to defend themselves against predators. Feeding experiments with a deuterated precursor ([(2)H(5)]8-hydroxygeraniol 9) and in vitro isotope exchange experiments with defensive secretion in (2)H(2)O revealed differences in the cyclisation of the ultimate precursor 8-oxogeranial (8) to 1, between members of the genus Gastrophysa and all other species. In P. cochleariae, H. marginella and P. vulgatissima 1 is most likely produced by a Rauhut-Currier-type cyclisation via a "transoid dienamine", with loss of a single deuterium atom from C(4) of the precursor. In contrast, members of the genus Gastrophysa cyclise 8 via a "cisoid dienamine" intermediate, with exchange of all three deuterium atoms from the methyl group at C(3). To study whether the different cyclisation modes influence the stereochemistry of 1, the absolute configuration of 1 of the larvae was determined by GC-MS on a chiral column. In accordance with literature (J. Meinwald, T. H. Jones, J. Am. Chem. Soc. 1978, 100, 1883 and N. Shimizu, R. Yakumaru, T. Sakata, S. Shimano, Y. Kuwahara, J. Chem. Ecol. 2012, 38, 29), we found (5S,8S)-chrysomelidial (1) in H. marginella and P. vulgatissima, but P. cochleariae and all investigated members of the genus Gastrophysa synthesise (5R,8R)-chrysomelidial (1).

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Section: Resultssupporting

confidence: 83%

“…[11,12] Finally, cyclisation of the acyclic dialdehyde 8 generates the iridoid 1, most likely via a transient plagiodial-type intermediate that is not observed in the secretion. Whether this cyclisation and isomerisation sequence requires two discrete enzymes (Scheme 2) or only a single cyclase (catalysing both steps) remains unknown.…”

Section: Introductionmentioning

confidence: 99%

Beetles Do It Differently: Two Stereodivergent Cyclisation Modes in Iridoid‐Producing Leaf‐Beetle Larvae

et al. 2013

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“…Other beetles known to produce iridoids are the Chloridolum loochooanum (long-horn beetle) [35] and the carnivorous feeding Philonthus spp. (rove beetles) [36]. One of the first insects discovered to contain iridoids was the eponymous ant Iridomyrmex spp.…”

Section: Discussionmentioning

confidence: 99%

Independently recruited oxidases from the glucose-methanol-choline oxidoreductase family enabled chemical defences in leaf beetle larvae (subtribe Chrysomelina) to evolve

et al. 2014

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Larvae of the leaf beetle subtribe Chrysomelina sensu stricto repel their enemies by displaying glandular secretions that contain defensive compounds. These repellents can be produced either de novo (iridoids) or by using plant-derived precursors (e.g. salicylaldehyde). The autonomous production of iridoids, as in Phaedon cochleariae, is the ancestral chrysomeline chemical defence and predates the evolution of salicylaldehyde-based defence. Both biosynthesis strategies include an oxidative step of an alcohol intermediate. In salicylaldehyde-producing species, this step is catalysed by salicyl alcohol oxidases (SAOs) of the glucose-methanol-choline (GMC) oxidoreductase superfamily, but the enzyme oxidizing the iridoid precursor is unknown. Here, we show by in vitro as well as in vivo experiments that P. cochleariae also uses an oxidase from the GMC superfamily for defensive purposes. However, our phylogenetic analysis of chrysomeline GMC oxidoreductases revealed that the oxidase of the iridoid pathway originated from a GMC clade different from that of the SAOs. Thus, the evolution of a host-independent chemical defence followed by a shift to a host-dependent chemical defence in chrysomeline beetles coincided with the utilization of genes from different GMC subfamilies. These findings illustrate the importance of the GMC multi-gene family for adaptive processes in plant-insect interactions.

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“…6 and 7). In the case of the natural O-glucoside, such an extreme accumulation does not occur, because the glucoside is rapidly cleaved and further transformed into iridoids (27). All transports systems display a very high selectivity and are obviously evolutionarily adapted to the class of compounds to be sequestered.…”

Section: Discussionmentioning

confidence: 99%

Selective transport systems mediate sequestration of plant glucosides in leaf beetles: A molecular basis for adaptation and evolution

Kuhn

Pettersson

Feld

et al. 2004

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

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Chrysomeline larvae respond to disturbance and attack by everting dorsal glandular reservoirs, which release defensive secretions. The ancestral defense is based on the de novo synthesis of monoterpene iridoids. The catabolization of the host-plant O-glucoside salicin into salicylaldehyde is a character state that evolved later in two distinct lineages, which specialized on Salicaceae. By using two species producing monoterpenes (Hydrothassa marginella and Phratora laticollis) and two sequestering species (Chrysomela populi and Phratora vitellinae), we studied the molecular basis of sequestration by feeding the larvae structurally different thioglucosides resembling natural O-glucosides. Their accumulation in the defensive systems demonstrated that the larvae possess transport systems, which are evolutionarily adapted to the glycosides of their host plants. Minor structural modifications in the aglycon result in drastically reduced transport rates of the test compounds. Moreover, the ancestral iridoid-producing leaf beetles already possess a fully functional import system for an early precursor of the iridoid defenses. Our data confirm an evolutionary scenario in which, after a host-plant change, the transport system of the leaf beetles may play a pivotal role in the adaptation on new hosts by selecting plant-derived glucosides that can be channeled to the defensive system.

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Iridoid biosynthesis in staphylinid rove beetles (Coleoptera: Staphylinidae, Philonthinae)

Cited by 24 publications

References 22 publications

Beetles Do It Differently: Two Stereodivergent Cyclisation Modes in Iridoid‐Producing Leaf‐Beetle Larvae

Beetles Do It Differently: Two Stereodivergent Cyclisation Modes in Iridoid‐Producing Leaf‐Beetle Larvae

Independently recruited oxidases from the glucose-methanol-choline oxidoreductase family enabled chemical defences in leaf beetle larvae (subtribe Chrysomelina) to evolve

Selective transport systems mediate sequestration of plant glucosides in leaf beetles: A molecular basis for adaptation and evolution

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