{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1361137045985381376.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/hlca.19770600336"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fhlca.19770600336"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/hlca.19770600336"}},{"identifier":{"@type":"DOI","@value":"10.1002/chin.197731320"}},{"identifier":{"@type":"PMID","@value":"863724"}}],"dc:title":[{"@value":"Gephyrotoxins, Histrionicotoxins and Pumiliotoxins from the Neotropical Frog <i>Dendrobates histrionicus</i>"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>The structure and absolute configuration of a new acetylenic alkaloid gephyrotoxin isolated from skin extracts of the Colombian frog <jats:italic>Dendrobates histrionicus</jats:italic>, has been determined by Röntgen‐ray crystallography. Gephyrotoxin, previously referred to as HTX‐D, is a novel tricyclic alkaloid, [1 <jats:italic>S</jats:italic>, 3a<jats:italic>S</jats:italic>, 5a<jats:italic>S</jats:italic>, 6<jats:italic>S</jats:italic>(<jats:italic>Z</jats:italic>), 9a <jats:italic>R</jats:italic>, 10 <jats:italic>R</jats:italic>]dodeca‐hydro‐6‐(2‐penten‐4‐yl)pyrrolo[1,2‐a]quinoline‐1‐ethanol. Dihydrogephyrotoxin, a minor skin constituent, contains a 6‐(2,4‐pentadienyl)substituent. Two further spiropiperidine alkaloids related in structure to histrionicotoxin, (6 <jats:italic>R</jats:italic>[6α[2<jats:italic>S</jats:italic>*(<jats:italic>Z</jats:italic>)],[7β(<jats:italic>Z</jats:italic>), 8α]]7‐(1‐buten‐3‐ynyl)‐2‐(2‐penten‐4‐ynyl)‐1‐aza<jats:italic>spiro</jats:italic> [5.5]undecan‐8‐ol), have been isolated from <jats:italic>Dendrobates histrionicus</jats:italic>: allodihydrohistrionicotoxin which differs from histrionicotoxin in having a 2‐(4‐pentynyl)‐substituent, while allotetrahydrohistrio‐nicotoxin, a minor constituent, has 2‐(4‐pentynyl)‐ and 7‐(1,3‐butadienyl)‐substituents. Three alkaloids related in structure to pumiliotoxin C, ([2 <jats:italic>S</jats:italic>, 4a <jats:italic>S</jats:italic>, 5<jats:italic>R</jats:italic>, 8a <jats:italic>R</jats:italic>]5‐methyl‐2‐<jats:italic>n</jats:italic>‐propyl‐<jats:italic>cis</jats:italic>‐decahydroquinoline), have been isolated from <jats:italic>Dendrobates histrionicus</jats:italic>. These alkaloids, with molecular weights of 195, 223, and 269, have, respectively, a 2‐butylsubstituent, 2‐propyl and 5‐propyl‐substituents, and 2‐(3,4‐pentadienyl) and 5‐(2‐penten‐4‐ynyl)‐substituents. The last compound was hydrogenated to a dodecahydro‐derivative identical in molecular weight, but not in other properties, with authentic dodecahydro‐8‐deoxy‐histrionicotoxin, which was prepared from histrionicotoxin. Gephyrotoxin, in contrast to histrionicotoxin and pumiliotoxin C, is a muscarinic antagonist.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1381137045985381376","@type":"Researcher","foaf:name":[{"@value":"J. W. Daly"}]},{"@id":"https://cir.nii.ac.jp/crid/1381137045985381379","@type":"Researcher","foaf:name":[{"@value":"B. Witkop"}]},{"@id":"https://cir.nii.ac.jp/crid/1381137045985381380","@type":"Researcher","foaf:name":[{"@value":"T. Tokuyama"}]},{"@id":"https://cir.nii.ac.jp/crid/1381137045985381378","@type":"Researcher","foaf:name":[{"@value":"T. Nishikawa"}]},{"@id":"https://cir.nii.ac.jp/crid/1381137045985381377","@type":"Researcher","foaf:name":[{"@value":"I. L. Karle"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"0018019X"},{"@type":"EISSN","@value":"15222675"},{"@type":"PISSN","@value":"00092975"},{"@type":"EISSN","@value":"21992924"}],"prism:publicationName":[{"@value":"Helvetica Chimica Acta"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"1977-04-20","prism:volume":"60","prism:number":"3","prism:startingPage":"1128","prism:endingPage":"1140"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fhlca.19770600336"},{"@id":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/hlca.19770600336"}],"createdAt":"2004-12-24","modifiedAt":"2023-10-19","foaf:topic":[{"@id":"https://cir.nii.ac.jp/all?q=Magnetic%20Resonance%20Spectroscopy","dc:title":"Magnetic Resonance Spectroscopy"},{"@id":"https://cir.nii.ac.jp/all?q=Molecular%20Weight","dc:title":"Molecular Weight"},{"@id":"https://cir.nii.ac.jp/all?q=Alkaloids","dc:title":"Alkaloids"},{"@id":"https://cir.nii.ac.jp/all?q=Muscarine","dc:title":"Muscarine"},{"@id":"https://cir.nii.ac.jp/all?q=Quinolines","dc:title":"Quinolines"},{"@id":"https://cir.nii.ac.jp/all?q=Animals","dc:title":"Animals"},{"@id":"https://cir.nii.ac.jp/all?q=Hydrogenation","dc:title":"Hydrogenation"},{"@id":"https://cir.nii.ac.jp/all?q=Anura","dc:title":"Anura"},{"@id":"https://cir.nii.ac.jp/all?q=Crystallization","dc:title":"Crystallization"},{"@id":"https://cir.nii.ac.jp/all?q=Toxins,%20Biological","dc:title":"Toxins, Biological"}],"relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360567179944338688","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Two‐step Synthesis of Multi‐Substituted Amines by Using an <i>N</i>‐Methoxy Group as a Reactivity Control Element"}]},{"@id":"https://cir.nii.ac.jp/crid/1360574096272344832","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Total Synthesis of (±)‐Gephyrotoxin by Amide‐Selective Reductive Nucleophilic Addition"}]},{"@id":"https://cir.nii.ac.jp/crid/1360848658559665408","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Total synthesis of complex alkaloids by nucleophilic addition to amides"}]},{"@id":"https://cir.nii.ac.jp/crid/1390001204143489664","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Total Syntheses of (±)-Gephyrotoxin and (±)-Perhydrogephyrotoxin"},{"@value":"BCSJ Award Article : Total Syntheses of (±)-Gephyrotoxin and (±)-Perhydrogephyrotoxin"},{"@value":"ChemInform Abstract: Total Syntheses of (.+‐.)‐Gephyrotoxin and (.+‐.)‐Perhydrogephyrotoxin."}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1002/hlca.19770600336"},{"@type":"OPENAIRE","@value":"doi_dedup___::da584285d9fe047680463eb7e545fb24"},{"@type":"CROSSREF","@value":"10.1246/bcsj.20140398_references_DOI_QUa25WZwL6OuIJBMXCYoRCfQIxw"},{"@type":"CROSSREF","@value":"10.1002/chem.201402231_references_DOI_QUa25WZwL6OuIJBMXCYoRCfQIxw"},{"@type":"CROSSREF","@value":"10.1002/anie.201308905_references_DOI_QUa25WZwL6OuIJBMXCYoRCfQIxw"},{"@type":"CROSSREF","@value":"10.1039/c8ob00733k_references_DOI_QUa25WZwL6OuIJBMXCYoRCfQIxw"}]}