Nitropolyzonamine: A spirocyclic nitro compound from the defensive glands of a milliped ()

Meinwald, Jerrold; Smolanoff, Joel; McPhail, Andrew T.; Miller, Richard W.; Eisner, Thomas; Hicks, Karen

doi:10.1016/0040-4039(75)80013-x

Cited by 46 publications

(38 citation statements)

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“…Millipede allomones include benzoquinones, phenols, benzaldehyde/hydrogen cyanide, and alkaloids (Eisner et al, 1978 and references therein). Three groups of alkaloids are known from millipedes as follows: (1) the glomerins (Ia & b) from millipedes of the genera Glomeris and Loboglomeris (Order: Glomerida, Family: Glomeridae) (Schildknecht et al, 1967 and reference therein), (2) the terpenoid alkaloids polyzonimine (II) and nitropolyzonamine (III) from the millipede Polyzonium rosalbum [now Petaserpes crytocephalus] (Order: Polyzoniida, Family: Polyzoniidae) (Meinwald et al, 1975 and reference therein), and (3) the terpenoid alkaloid buzonamine (IV) from a millipede of the genus Buzonium (Order: Polyzoniida, Family: Polyzoniidae) (Wood et al, 2000) (Figure 1). Certain poison frogs/toads of the families Dendrobatidae, Mantellidae, and Bufonidae contain spiropyrrolizidine alkaloids (Figure 1; Va & b and VI) (Daly et al, 1994 and references therein) with carbon skeletons identical to those of the millipede alkaloid nitropolyzonamine.…”

Section: Introductionmentioning

confidence: 99%

A Siphonotid Millipede (Rhinotus) as the Source of Spiropyrrolizidine Oximes of Dendrobatid Frogs

et al. 2003

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Abstract-Poison frogs of the neotropical family Dendrobatidae contain a wide variety of lipophilic alkaloids, which are accumulated from alkaloidcontaining arthropods. A small millipede, Rhinotus purpureus (Siphonotidae), occurs microsympatrically with the dendrobatid frog Dendrobates pumilio on Isla Bastimentos, Bocas del Toro Province, Panamá. Methanol extracts of this millipede contain the spiropyrrolizidine O-methyloxime 236, an alkaloid previously known only from skin extracts of poison frogs, including populations of D. pumilio. Thus, R. purpureus represents a likely dietary source of such alkaloids in dendrobatid frogs.

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Section: Introductionmentioning

confidence: 99%

A Siphonotid Millipede (Rhinotus) as the Source of Spiropyrrolizidine Oximes of Dendrobatid Frogs

et al. 2003

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“…However, this must be proved. The structures 1 and 2 proposed for these milliped alkaloids were confirmed by the synthesis of their racemates 2,3,5 . Only a single existing asymmetric synthesis of (+)-1 with 68% ee could not tell us anything about its absolute configuration 6 .…”

Section: Introductionmentioning

confidence: 82%

“…-Optical rotation: Jasco P-1020. 3 ) at 0°C, and the reaction mixture was stirred for 1.5 h at room temperature. The excess LiAlH 4 was destroyed by the careful addition of water (6.5 cm 3 ), 15% aq.…”

Section: Generalmentioning

confidence: 99%

“…In 1975, in the course of their studies on compounds from the defensive glands of a milliped Polyzonium rosalbum, Meinwald, Eisner and their respective co-workers isolated and identified the following two nitrogen-containing spirocyclic compounds 2,3 . (+)-Polyzonimine {6,6-dimethyl-2-azaspiro [4.4]non-1-ene (1)} was isolated as a volatile insect repellent, which acts as a topical irritant to predating insects such as ants and cockroaches 2 (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Enantioselective synthesis of (+)-polyzonimine, defensive monoterpene alkaloid produced by a milliped Polyzonium rosalbum, and determination of its S absolute configuration by Its conversion to (4S,5R,6S)-(+)-nitropolyzonamine

Takagi¹,

Mori²

2000

J. Braz. Chem. Soc.

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A adição de Michael da enamina derivada do 2,2-dimetilciclopentanocarboxaldeído e do éter metílico do (S)-prolinol com o nitroetileno, forneceu o aduto correspondente em 75-76% ee, o qual foi convertido na (+)-polizonimina enantiomericamente pura, um espiro composto nitrogenado isolado das glândulas que contêm os compostos de defesa do "milliped" Polyzonium rosalbum. Através da conversão da (+)-polizonimina na (4S, 5R, 6S)-(+)-nitropolizonamina, foi possível estabelecer a configuração absoluta desta como sendo S.Asymmetric Michael addition of the enamine derived from 2,2-dimethylcyclopentanecarboxaldehyde and (S)-prolinol methyl ether to nitroethylene afforded the adduct of 75-76% ee, which finally yielded enantiomerically pure (+)-polyzonimine, a nitrogen-containing spirocyclic compound isolated from the defensive glands of a milliped, Polyzonium rosalbum. By converting (+)-polyzonimine into (4S,5R,6S)-(+)-nitropolyzonamine, the hitherto uncertain absolute configuration of the former was established as S.

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“…The first are the pyrrolizidine oximes (32), whose carbon skeleton is identical to that of nitropolyzonamine, an alkaloid from a small millipede (33). Indeed, raising the dendrobatid frog D. auratus in Panama on leaf-litter arthropods, gathered weekly, resulted in skin levels of the pyrrolizidine oxime 236 even higher than levels in wild-caught frogs from the leaf-litter site (34) (34).…”

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confidence: 99%

The chemistry of poisons in amphibian skin.

Daly

1995

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

247

155

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Poisons are common in nature, where they often serve the organism in chemical defense. Such poisons either are produced de novo or are sequestered from dietary sources or symbiotic organisms. Among vertebrates, amphibians are notable for the wide range of noxious agents that are contained in granular skin glands. These compounds include amines, peptides, proteins, steroids, and both water-soluble and lipid-soluble alkaloids. With the exception of the alkaloids, most seem to be produced de novo by the amphibian. The skin of amphibians contains many structural classes of alkaloids previously unknown in nature. These include the batrachotoxins, which have recently been discovered to also occur in skin and feathers of a bird, the histrionicotoxins, the gephyrotoxins, the decahydroquinolines, the pumiliotoxins and homopumiliotoxins, epibatidine, and the samandarines. Some amphibian skin alkaloids are clearly sequestered from the diet, which consists mainly of small arthropods. These include pyrrolizidine and indolizidine alkaloids from ants, tricyclic coccinellines from beetles, and pyrrolizidine oximes, presumably from millipedes. The sources of other alkaloids in amphibian skin, including the batrachotoxins, the decahydroquinolines, the histrionicotoxins, the pumiliotoxins, and epibatidine, are unknown. While it is possible that these are produced de novo or by symbiotic microorganisms, it appears more likely that they are sequestered by the amphibians from as yet unknown dietary sources.

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Nitropolyzonamine: A spirocyclic nitro compound from the defensive glands of a milliped ()

Cited by 46 publications

References 2 publications

A Siphonotid Millipede (Rhinotus) as the Source of Spiropyrrolizidine Oximes of Dendrobatid Frogs

A Siphonotid Millipede (Rhinotus) as the Source of Spiropyrrolizidine Oximes of Dendrobatid Frogs

Enantioselective synthesis of (+)-polyzonimine, defensive monoterpene alkaloid produced by a milliped Polyzonium rosalbum, and determination of its S absolute configuration by Its conversion to (4S,5R,6S)-(+)-nitropolyzonamine

The chemistry of poisons in amphibian skin.

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