Unexpected synthesis of conformationally restricted analogues of gamma-amino butyric acid (GABA): Mechanism elucidation by electrospray ionization mass spectrometry

dc.creatorFerraz, HMC
dc.creatorPereira, FLC
dc.creatorGoncalo, ERS
dc.creatorSantos, LS
dc.creatorEberlin, MN
dc.date2005
dc.date39083
dc.date2014-07-30T19:30:31Z
dc.date2015-11-26T17:51:05Z
dc.date2014-07-30T19:30:31Z
dc.date2015-11-26T17:51:05Z
dc.date.accessioned2018-03-29T00:34:27Z
dc.date.available2018-03-29T00:34:27Z
dc.identifierJournal Of Organic Chemistry. Amer Chemical Soc, v. 70, n. 1, n. 110, n. 114, 2005.
dc.identifier0022-3263
dc.identifierWOS:000226508600013
dc.identifier10.1021/jo048309e
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/73399
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/73399
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1289881
dc.descriptionFrom previous results with lower homologues, dehydroiodination of the three alkenyl-beta-enamino esters 3a-c was expected to provide six-membered N-heterocyclic products. The reactions of 3a-c with triethylamine are found to lead, however, to the unexpected stereoselective synthesis of the trisubstituted cyclopentane derivatives 4a-c, as confirmed by IR and NMR spectroscopy. Cyclopentanes 4a-c bear two chiral centers and a gamma-amino ester moiety, and are therefore conformationally restricted analogues of gamma-amino butyric acid (GABA), which is the major inhibitory neurotransmitter in the central nervous system. Use of electrospray ionization mass (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) allowed the key iminium ion intermediates 5a-c(+), as well as the protonated molecules of both the reactant and final products, [3a-c + H](+) and [4a-c + H](+), to be intercepted and structurally characterized. From these findings a mechanism for this unexpected but synthetically attractive and efficient stereoselective reaction is proposed.
dc.description70
dc.description1
dc.description110
dc.description114
dc.languageen
dc.publisherAmer Chemical Soc
dc.publisherWashington
dc.publisherEUA
dc.relationJournal Of Organic Chemistry
dc.relationJ. Org. Chem.
dc.rightsfechado
dc.sourceWeb of Science
dc.subjectBeta-dicarbonyl Compounds
dc.subjectCation Chain-reactions
dc.subjectChannel Ligands
dc.subjectEnamino Esters
dc.subjectDerivatives
dc.subject1,4-dihydropyridines
dc.subjectHomochirogenesis
dc.subject1,2,3-triazoles
dc.subjectIdentification
dc.subjectSubstitution
dc.titleUnexpected synthesis of conformationally restricted analogues of gamma-amino butyric acid (GABA): Mechanism elucidation by electrospray ionization mass spectrometry
dc.typeArtículos de revistas


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