Formal fusion of a pyrrole ring onto 2-pyridyl and 2-pyrimidyl cations: One-step gas-phase synthesis of indolizine and its derivatives

dc.creatorSparrapan, R
dc.creatorMendes, MA
dc.creatorCarvalho, M
dc.creatorEberlin, MN
dc.date2000
dc.dateJAN
dc.date2014-12-02T16:29:35Z
dc.date2015-11-26T16:40:02Z
dc.date2014-12-02T16:29:35Z
dc.date2015-11-26T16:40:02Z
dc.date.accessioned2018-03-28T23:23:49Z
dc.date.available2018-03-28T23:23:49Z
dc.identifierChemistry-a European Journal. Wiley-v C H Verlag Gmbh, v. 6, n. 2, n. 321, n. 326, 2000.
dc.identifier0947-6539
dc.identifierWOS:000084931200013
dc.identifier10.1002/(SICI)1521-3765(20000117)6:2<321
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/67039
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/67039
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/67039
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1272643
dc.descriptionTwo ortho-hetarynium ions, the 2-pyridyl and 2-pyrimidyl cations, react promptly with 1,3-dienes in the gas phase by annulation, formally by fusion, onto the ions of a pyrrole ring. This novel reaction proceeds through an initial polar [4 + 2(+)] cycloaddition across the C=N+ bond, followed by fast ring opening, a [1,4-H] shift, and finally a recyclization that results in a contraction of a six- to a five-membered ring and dissociation by the loss of a methyl radical. For the 2-pyridyl cation. this reaction yields ionized indolizines (pyrrolo[1,2-a]pyridines), while for the 2-pyrimidyl cation, it gives ionized pyrrolo[1,2-a]pyrimidines. The annulation reaction, performed in the rf-only collision quadrupole of a pentaquadrupole (QqQqQ) mass spectrometer, occurs readily with both 1,3-butadiene and isoprene, and is thermodynamically and kinetically favored as predicted by ab initio calculations. Ortho-hetarynium ions and 1,3-dienes provide, therefore, the two building blocks for the efficient one-step gas-phase synthesis of ionized bicyclic pyrrolo[1,2-a]pyridine (indolizine) and pyrrolo[1,2-a] pyrimidine, as well as their analogues and derivatives.
dc.description6
dc.description2
dc.description321
dc.description326
dc.languageen
dc.publisherWiley-v C H Verlag Gmbh
dc.publisherBerlin
dc.publisherAlemanha
dc.relationChemistry-a European Journal
dc.relationChem.-Eur. J.
dc.rightsfechado
dc.rightshttp://olabout.wiley.com/WileyCDA/Section/id-406071.html
dc.sourceWeb of Science
dc.subjectcycloadditions
dc.subjectheterocycles
dc.subjection-molecules reactions
dc.subjectmass spectroscopy
dc.subjectDiels-alder Cycloaddition
dc.subjectEven-electron Rule
dc.subjectMass-spectrometry
dc.subjectAcylium Ions
dc.subjectImmonium Ions
dc.subjectTransacetalization
dc.subject3d
dc.titleFormal fusion of a pyrrole ring onto 2-pyridyl and 2-pyrimidyl cations: One-step gas-phase synthesis of indolizine and its derivatives
dc.typeArtículos de revistas


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