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dc.contributor.authorBélanger, Guillaumefr
dc.contributor.authorLarouche-Gauthier, Robinfr
dc.contributor.authorMénard, Frédéricfr
dc.contributor.authorNantel, Miguelfr
dc.contributor.authorBarabé, Francisfr
dc.contributor.editorUniversité de Sherbrooke. Laboratoire de synthèse organique et de développement de stratégies de synthèsefr
dc.date.accessioned2020-08-24T20:41:12Z
dc.date.available2020-08-24T20:41:12Z
dc.date.created2006fr
dc.date.issued2020-08-24
dc.identifier.urihttp://hdl.handle.net/11143/17290
dc.description.abstractAbstract: Vilsmeier-Haack type cyclizations proved to be particularly efficient for generating parts of the polycyclic cores of many alkaloids, although only monocyclizations have so far been reported. With the goal of rapidly and efficiently constructing polycyclic alkaloids, we decided to exploit the Vilsmeier-Haack reaction by utilizing iminium ions successively generated and trapped with tethered nucleophiles. To develop such a strategy, we had to set the first cyclization. This constitutes a great challenge in itself because amide activation conditions are usually not compatible with tethered nucleophiles, except for indoles and aromatic rings which have already been reported. This paper describes the comprehensive study of intramolecular addition of silyl enol ethers, allylsilanes, and enamines to chemoselectively activated formamides, aliphatic amides, and lactams. Good to excellent yields were obtained for the 5-exo, 6-exo, and 6-endo modes of cyclization. Moreover, we demonstrated that the species in solution after the cyclization are iminium ions. This is highly encouraging for the development of bis-cyclization strategies. An expeditious total synthesis of (()-tashiromine is also reported.fr
dc.language.isoengfr
dc.relation.isformatofhttps://doi.org/10.1021/jo052141vfr
dc.relation.ispartofISSN:1520-6904fr
dc.relation.ispartofThe Journal of Organic Chemistryfr
dc.rightsAttribution - Pas d’Utilisation Commerciale - Pas de Modification 2.5 Canada*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/2.5/ca/*
dc.subjectEthersfr
dc.subjectAmidesfr
dc.subjectCyclizationfr
dc.subjectSubstitution reactionsfr
dc.subjectIonsfr
dc.titleIntramolecular additions of various π-nucleophiles to chemoselectively activated amides and application to the synthesis of (±)-tashirominefr
dc.typeArticlefr
dc.rights.holder© ACS Journal Publishingfr
udes.description.typestatusPost-publicationfr
udes.description.typepubRévisé et accepté par des pairsfr
udes.description.pages704–712fr
udes.description.period71(2)fr
udes.description.diffusionDiffusé par Savoirs UdeS, le dépôt institutionnel de l'Université de Sherbrookefr
dc.identifier.bibliographicCitationBélanger, G., Larouche-Gauthier, R., Ménard, F., Nantel, M., et Barabé, F. (2006). "Intramolecular additions of various π-nucleophiles to chemoselectively activated amides and application to the synthesis of (±)-tashiromine". The Journal of Organic Chemistry, 71(2), 704–712. https://doi.org/10.1021/jo052141vfr
udes.description.sourceThe Journal of Organic Chemistryfr
udes.autorisation.depottruefr
udes.description.ordreauteursBélanger, Guillaume; Larouche-Gauthier, Robin; Ménard, Frédéric; Nantel, Miguel; Barabé, Francisfr


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Attribution - Pas d’Utilisation Commerciale - Pas de Modification 2.5 Canada
Except where otherwise noted, this document's license is described as Attribution - Pas d’Utilisation Commerciale - Pas de Modification 2.5 Canada