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

DSpace/Manakin Repository

Show simple item record

dc.creator Vargas, Didier F.
dc.creator Larghi, Enrique Leandro
dc.creator Kaufman, Teodoro Saúl
dc.date.accessioned 2020-12-23T15:48:33Z
dc.date.available 2020-12-23T15:48:33Z
dc.date.issued 2019-10-16
dc.identifier.issn 2046-2069 es
dc.identifier.uri http://hdl.handle.net/2133/19543
dc.description A 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.description This 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.sponsorship Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT): PICT 2017-0149 es
dc.description.sponsorship Agencia Santafesina de Ciencia, Tecnología e Innovación (ASaCTeI): AC 2015-0005 es
dc.format application/pdf
dc.format.extent 33096–33106 es
dc.language.iso eng es
dc.publisher Royal Society of Chemistry es
dc.rights openAccess es
dc.rights.uri https://creativecommons.org/licenses/by/3.0/ *
dc.subject Ampullosine es
dc.subject 3-Methyl-isoquinoline-6-carboxylic Acid es
dc.subject Isoquinoline Alkaloid es
dc.subject Sepedonium ampullosporum es
dc.subject Permethylampullosine es
dc.subject Biopharmaceutics es
dc.title First total synthesis of ampullosine, a unique isoquinoline alkaloid isolated from Sepedonium ampullosporum, and of the related permethylampullosine es
dc.type article
dc.type artículo
dc.type publishedVersion
dc.rights.holder Universidad Nacional de Rosario es
dc.rights.holder Royal Society of Chemistry es
dc.rights.holder Vargas, Didier F. es
dc.rights.holder Larghi, Enrique Leandro es
dc.rights.holder Kaufman, Teodoro Saúl es
dc.relation.publisherversion https://pubs.rsc.org/en/content/articlelanding/2019/RA/C9RA06839B#!divAbstract es
dc.relation.publisherversion https://doi.org/10.1039/c9ra06839b es
dc.rights.text Attribution 3.0 Unported (CC BY 3.0) es
dc.citation.title RSC Advances es
dc.citation.volume (57) es
dc.description.fil Fil: Vargas, Didier F. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR -CONICET); Argentina. es
dc.description.fil Fil: Larghi, Enrique Leandro. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR -CONICET); Argentina. es
dc.description.fil Fil: Kaufman, Teodoro Saúl. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR -CONICET); Argentina. es
dc.type.collection articulo
dc.type.version publishedVersion es


Files in this item

The following license files are associated with this item:

This item appears in the following Collection(s)

Show simple item record

openAccess Except where otherwise noted, this item's license is described as openAccess

My Account


Search DSpace


Browse