Structural characterization of saturated pyrrolizidine alkaloids from Heliotropium transalpinum var. transalpinum Vell by NMR spectroscopy and theoretical calculations

Medina, Janaina C.M.; Gauze, Gisele F.; Vidotti, Gentil J.; Sarragiotto, María Helena; Basso, Ernani A.; Peixoto, Juliana Luna Bilheiro

doi:10.1016/j.tetlet.2009.03.074

Cited by 20 publications

(15 citation statements)

References 15 publications

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“…The PA profile of H. transalpinum has already been described by Trigo et al 14 We did not find the PAs transalpinecine, subulacine, and their stereoisomers, as given by Medina et al 25 As other arctiines that feed on PA plants as larvae, [12][13][14] our results showed that S. figulina also uptakes these defensive compounds from its host plant. Although no analyses were performed to check if PAs are present only in the N-oxide form, we have made this assumption, since it has occurred in other arctiines studied.…”

Section: Discussionsupporting

confidence: 73%

“…23,24 These species, as well as other Boraginaceae species, show PAs in their tissues. 14,25,26 Scearctia figulina sampling and rearing Gregarious moth eggs (87 ± 11 eggs, n = 10, mean ± standard error) were sampled in individuals of H. transalpinum in an open area near the Animal Biology Department, Institute of Biology at the State University of Campinas, Campinas, São Paulo, Brazil (22°49'15.38"S, 047°04'8.87"W). After eclosion, gregarious larvae were kept in plastic containers (18 cm high, 11 cm diameter, 10-15 larvae per container) until pupation in an incubator at 27 ° C, L:D 12:12 photoperiod, with no relative humidity control.…”

Section: Studied Organismsmentioning

confidence: 99%

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Pyrrolizidine Alkaloids in the Pericopine MothScearctia figulina(Erebidae: Arctiinae): Metabolism and Chemical Defense

Martins

Trigo

2016

Journal of the Brazilian Chemical Society

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Pyrrolizidine alkaloids (PAs) are defensive compounds present in several plant families. However, some specialist herbivore insects have overcome these toxic compounds and sequester PAs converted to N-oxide as a defense against predators and a precursor of male sexual pheromones. In this context, we investigated PA sequestration by the specialist pericopine moth Scearctia figulina (Erebidae: Arctiinae), which feeds on leaves of Heliotropium transalpinum (Boraginaceae) as larvae. Additionally, we examined the role of PAs against different predators. The PAs sequestered from the host plant were metabolized by larvae and transferred to adults via two main pathways: (i) rinderine and its acetyl derivative (7S,3'R) were epimerized to intermedine (7R,3'R) and lycopsamine (7R,3'S), and (ii) insect PAs were biosynthesized from necine bases obtained from plant-acquired PAs, with necic acids of insect origin. Both metabolic products may be related to the biosynthesis of 7R male pheromone and to chemical defense. Larvae and adults were chemically protected against the spiders Nephila clavipes and Lycosa erythrognatha and the chick Gallus gallus, and this defense may be associated to PAs. Keywords: callimorphine, Heliotropium transalpinum, insect PAs, lycopsamine, predation IntroductionPyrrolizidine alkaloids, particularly 1,2-dehydropyrrolizidines (hereafter PAs), are powerful defensive compounds in several plant taxa, such as Eupatorieae and Senecioneae (Asteraceae), Boraginaceae, and Crotalarieae (Leguminosae).1,2 However, specialized herbivores, such as arctiine moths, danaine and ithomiine butterflies and chrysomeline beetles, among others, are able to cope with pro-toxic free-base PAs from these plants, converting them into non-toxic N-oxides.3,4 These insects sequester PA N-oxides, incorporating them into their tissues, and this renders chemical protection against predators and parasitoids.1,5 Arctiine moths and danaine and ithomiine butterflies also use PAs as precursors of male sexual pheromones, such as the dihydropyrrolizine hydroxydanaidal.6-8 PAs were also recorded in the grasshopper Zonocerus variegatus, the aphid Aphis jacobaeae, the bug Largus rufipennis, and the coccide Ceroplastes albolineatus.1 PA-containing insects are generally aposematic, i.e., their unpalatability is associated with warning signals alerting predators of this trait; warning signals can be visual, sonorous, or odorant. 9Among arctiine moths, 10 PAs were found in the tribes Amerilini and Arctiini (subtribes Callimorphina, Arctiina, Pericopina, Ctenuchina, Euchromiina, and Phaegopterina), but not in Lithosiini and Syntomini. 11 Three PA acquisition strategies were found in these moths: (i) PA-obtained as adults, (ii) PA-specialist feeding as larvae, and (iii) PA-generalist feeding as larvae.11 In the first syndrome, adults either feeding on nectar containing PAs or display a pharmacophagous behavior, or obtaining the alkaloid visiting withered PA-containing plants. 2,12,13 This syndrome was widely found in Ctenuchina, Euchromiina, an...

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Section: Discussionsupporting

confidence: 73%

Section: Studied Organismsmentioning

confidence: 99%

Pyrrolizidine Alkaloids in the Pericopine MothScearctia figulina(Erebidae: Arctiinae): Metabolism and Chemical Defense

Martins

Trigo

2016

Journal of the Brazilian Chemical Society

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“…成部分 [1] . 在过去的数年中, 它的衍生物在消炎 [2] 、镇痛 [3] 、抗糖尿 [4] 、抗焦虑 [5] 、抗肿瘤 [6] 、感光 [7] 、抗神经激肽-1 (NK1) [8] 等方面中得到了广泛的应用.…”

Section: 吡咯里嗪是一些具有生物活性的生物碱的重要组unclassified

Synthesis of Novel Spiro[pyrazole-pyrrolizin] Derivatives via 1,3-Dipolar Cycloaddition of Nitrilimine

胡小莲¹,

刘彬²,

刘浩冲³

et al. 2013

Chin. J. Org. Chem.

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“…Pyrrolizidine alkaloids (PAs) are of particular interest for synthetic chemists because of the panel of biological activities associated with their relatively simple structure . In 2009, Vidotti's group reported the isolation and characterization of transalpinecine (1β,2β‐dihydroxy‐1α‐hydroxymethyl‐8α‐pyrrolizidine), a new saturated PA extracted from Heliotropium transalpinum var. transalpinum Vell .…”

Section: Introductionmentioning

confidence: 99%

“…While antineoplastic and antiviral activities of subulacine were evaluated,[4a] the other compounds described by Vidotti were never submitted to any biological evaluation . However, these pyrrolizidines alkaloids can be seen as analogs of carbon‐branched pyrrolidine iminosugars described by Best et al, especially isoLAB (Figure ), which proved to partially rescue the defective function of F508del‐cystic fibrosis transmembrane conductance regulator (F508del‐CFTR) responsible for cystic fibrosis .…”

Section: Introductionmentioning

confidence: 99%

Transalpinecine and Analogues: First Total Synthesis, Stereochemical Revision and Biological Evaluation

et al. 2019

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The first total synthesis of transalpinecine, a pyrrolizidine alkaloid extracted from Heliotropium transalpinum is reported. The concise synthetic route developed towards these unusual iminosugar‐like natural compounds relies on an intramolecular Morita–Baylis–Hillman reaction. The four diastereoisomers of transalpinecine, as well as the two diastereoisomers of the parent epoxide subulacine, were prepared. 1H NMR‐based stereochemical assignment of these different diastereoisomers was substantiated by quantum calculations of NMR shifts and coupling constants, allowing revision of the initially reported transalpinecine structure. One of these synthetic compounds significantly potentiates the activity of the F508del‐CFTR corrector VX‐809.

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Structural characterization of saturated pyrrolizidine alkaloids from Heliotropium transalpinum var. transalpinum Vell by NMR spectroscopy and theoretical calculations

Cited by 20 publications

References 15 publications

Pyrrolizidine Alkaloids in the Pericopine MothScearctia figulina(Erebidae: Arctiinae): Metabolism and Chemical Defense

Pyrrolizidine Alkaloids in the Pericopine MothScearctia figulina(Erebidae: Arctiinae): Metabolism and Chemical Defense

Synthesis of Novel Spiro[pyrazole-pyrrolizin] Derivatives via 1,3-Dipolar Cycloaddition of Nitrilimine

Transalpinecine and Analogues: First Total Synthesis, Stereochemical Revision and Biological Evaluation

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