First total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosine

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dc.citation.titleRSC Advanceses
dc.citation.volume(57)es
dc.creatorVargas, Didier F.
dc.creatorLarghi, Enrique Leandro
dc.creatorKaufman, Teodoro Saúl
dc.date.accessioned2020-12-23T15:48:33Z
dc.date.available2020-12-23T15:48:33Z
dc.date.issued2019-10-16
dc.descriptionA straightforward and convenient approach toward the first total synthesis of ampullosine, a structurally unique 3-methylisoquinoline alkaloid isolated from Sepedonium ampullosporum, is reported. Access to the related O-methyl ampullosine methyl ester from a common intermediate is also disclosed. The synthetic sequence toward the natural product comprised a Kolbe-type carboxylation of 3,5- dihydroxybenzoic acid and further esterification of the diacid, followed by masking of one of the phenols through selective ester reduction and subsequent acetonide formation. Installation of the three-carbon atom required for the 3-methylpyridine ring was performed by triflation of the remaining free phenol and a Pd-catalyzed Suzuki–Miyaura reaction with potassium E-propenyltrifluoroborate. Deprotection of the acetonide, followed by partial oxidation of the benzylic alcohol to the salicylaldehyde, O-methylation of the free phenol and hydrazonation of the resulting ortho-anisaldehyde derivative gave a hydrazonebased 1-azatriene. This was further subjected to 6p-azaelectrocyclization to afford permethylampullosine (11 steps, 14% overall yield), whereas exhaustive demethylation with AlI3 generated in situ gave ampullosine (12 steps, 3.2% global yield).es
dc.descriptionThis is a post-peer-review, pre-copyedit version of an article published in RSC Advances. The final authenticated version is available online at: https://doi.org/10.1039/c9ra06839b
dc.description.filFil: Vargas, Didier F. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR -CONICET); Argentina.es
dc.description.filFil: Larghi, Enrique Leandro. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR -CONICET); Argentina.es
dc.description.filFil: Kaufman, Teodoro Saúl. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR -CONICET); Argentina.es
dc.description.sponsorshipAgencia Nacional de Promoción Científica y Tecnológica (ANPCyT): PICT 2017-0149es
dc.description.sponsorshipAgencia Santafesina de Ciencia, Tecnología e Innovación (ASaCTeI): AC 2015-0005es
dc.formatapplication/pdf
dc.format.extent33096–33106es
dc.identifier.issn2046-2069es
dc.identifier.urihttp://hdl.handle.net/2133/19543
dc.language.isoenges
dc.publisherRoyal Society of Chemistryes
dc.relation.publisherversionhttps://pubs.rsc.org/en/content/articlelanding/2019/RA/C9RA06839B#!divAbstractes
dc.relation.publisherversionhttps://doi.org/10.1039/c9ra06839bes
dc.rightsopenAccesses
dc.rights.holderUniversidad Nacional de Rosarioes
dc.rights.holderRoyal Society of Chemistryes
dc.rights.holderVargas, Didier F.es
dc.rights.holderLarghi, Enrique Leandroes
dc.rights.holderKaufman, Teodoro Saúles
dc.rights.textAttribution 3.0 Unported (CC BY 3.0)es
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/*
dc.subjectAmpullosinees
dc.subject3-Methyl-isoquinoline-6-carboxylic Acides
dc.subjectIsoquinoline Alkaloides
dc.subjectSepedonium ampullosporumes
dc.subjectPermethylampullosinees
dc.subjectBiopharmaceuticses
dc.titleFirst total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosinees
dc.typearticle
dc.typeartículo
dc.typepublishedVersion
dc.type.collectionarticulo
dc.type.versionpublishedVersiones

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