The gas-phase Meerwein reaction

dc.creatorMoraes, LAB
dc.creatorEberlin, MN
dc.date2000
dc.date37681
dc.date2014-12-02T16:28:48Z
dc.date2015-11-26T16:38:22Z
dc.date2014-12-02T16:28:48Z
dc.date2015-11-26T16:38:22Z
dc.date.accessioned2018-03-28T23:21:39Z
dc.date.available2018-03-28T23:21:39Z
dc.identifierChemistry-a European Journal. Wiley-v C H Verlag Gmbh, v. 6, n. 5, n. 897, n. 905, 2000.
dc.identifier0947-6539
dc.identifierWOS:000085815200017
dc.identifier10.1002/(SICI)1521-3765(20000303)6:5<897
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/73682
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/73682
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/73682
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1272250
dc.descriptionA systematic investigation of a novel epoxide and thioepoxide ring expansion reaction promoted by gaseous acylium and thioacylium ions is reported. As ab initio calculations predict, and O-18-labeling and MS3 pentaquadrupole experiments demonstrate, the reaction proceeds by initial O(S)-acylation of the (thio)epoxides followed by rapid intramolecular nucleophilic attack that results in three-to-five-membered ring expansion, and forms cyclic 1,3-dioxolanylium, 1,3-oxathiolanylium, or 1,3-dithiolanylium ions. This gas-phase reaction is analogous to a condensed-phase reaction long since described by H. Meerwein (Chem. Ber. 1955, 67, 374), and is termed as "the gas-phase Meerwein reaction"; it occurs often to great extents or even exclusively, but in some cases, particularly for the most basic (thio)epoxides and the most acidic (thio)acylium ions, proton transfer (eventually hydride abstraction) competes efficiently, or even dominates. When (thio)epoxides react with (thio)acylium ions, the reaction promotes O(S)-scrambling; when epoxides react with thioacylium ions and the adducts are dissociated, it promotes S/O replacement. An analogous four-to-six-membered ring expansion also occurs predominantly in reactions of trimethylene oxide with acylium and thioacylium ions.
dc.description6
dc.description5
dc.description897
dc.description905
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.subjectepoxides
dc.subjectthioepoxides
dc.subjectacylium ions
dc.subjectthioacylium ions
dc.subjection-molecule reactions
dc.subjectmass spectroscopy
dc.subjectIon-molecule Reactions
dc.subjectAcylium Ions
dc.subjectMass-spectrometry
dc.subjectCyclic Acetals
dc.subjectCations
dc.subjectTransacetalization
dc.subjectSubstitution
dc.subjectKetals
dc.subject3d
dc.titleThe gas-phase Meerwein reaction
dc.typeArtículos de revistas


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