Experimental and computational evidence for ?-lactone intermediates in the addition of aqueous bromine to disodium dimethyl-maleate and -fumarate

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dc.contributor.authorPirinccioglu, Necmettin
dc.contributor.authorRobinson, James J.
dc.contributor.authorMahon, Mary F.
dc.contributor.authorBuchanan, J. Grant
dc.contributor.authorWilliams, Ian H.
dc.date.accessioned2024-04-24T16:24:04Z
dc.date.available2024-04-24T16:24:04Z
dc.date.issued2007
dc.departmentDicle Üniversitesien_US
dc.description.abstractStructural analysis of the bromo-beta-lactones obtained by addition of bromine to aqueous solutions of disodium 2,3-dimethylmaleate and 2,3-dimethylfumarate reveals stereochemistries opposite to those originally assigned in 1937: cis alkene yields erythro lactone, and trans alkene yields threo lactone. B3LYP/6-31+G(d) calculations using a PCM description of aqueous solvation confirm the validity of our proposed mechanism, in which the first-formed intermediate in each case is an a-lactone. The cyclic bromonium species is not an intermediate. An alternative pathway leading directly from cis alkene to cis lactone, via an unusual frontside displacement mechanism, is over 20 kJ mol(-1) higher in free energy. Hydrolysis of the bromo-beta-lactones yields bromohydrins whose stereochemistries as determined by X-ray crystallography indicate stereospecific formation by acyl-oxygen cleavage of the lactone ring, again contrary to the original view.en_US
dc.identifier.doi10.1039/b711538e
dc.identifier.endpage4009en_US
dc.identifier.issn1477-0520
dc.identifier.issn1477-0539
dc.identifier.issue24en_US
dc.identifier.pmid18043806
dc.identifier.scopus2-s2.0-36749044733
dc.identifier.scopusqualityQ2
dc.identifier.startpage4001en_US
dc.identifier.urihttps://doi.org/10.1039/b711538e
dc.identifier.urihttps://hdl.handle.net/11468/16463
dc.identifier.volume5en_US
dc.identifier.wosWOS:000251274700016
dc.identifier.wosqualityQ1
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoenen_US
dc.publisherRoyal Soc Chemistryen_US
dc.relation.ispartofOrganic & Biomolecular Chemistry
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subject[No Keyword]en_US
dc.titleExperimental and computational evidence for ?-lactone intermediates in the addition of aqueous bromine to disodium dimethyl-maleate and -fumarateen_US
dc.titleExperimental and computational evidence for ?-lactone intermediates in the addition of aqueous bromine to disodium dimethyl-maleate and -fumarate
dc.typeArticleen_US

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