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dc.creatorDrakulić, Branko
dc.creatorMarinković, Aleksandar D.
dc.creatorJuranić, Ivan
dc.date.accessioned2020-03-12T12:35:24Z
dc.date.available2020-03-12T12:35:24Z
dc.date.issued2012
dc.identifier.issn00404039
dc.identifier.urihttp://cer.ihtm.bg.ac.rs/handle/123456789/3438
dc.description.abstractRate constants for the esterification of eleven 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane in ethanol at 30 C were determined, and correlated with substituent constants using classical Hammett and related methods. Statistically valid results for the para-substituted compounds were obtained by the Swain–Lupton approach. The compounds studied had significant conformational mobility due to seven rotatable bonds in their backbone. Going beyond the classical Hammett approach, we established a relatively fast procedure to find the optimal conformations that can be used in linear free-energy relationships, combining molecular dynamics with semiempirical calculations, and calculations using a higher level of theory (DFT and MP2). Fair correlations were observed with frontier orbitals, allowing inclusion of ortho-substituted derivatives and clarifying artifact-like data, as perceived by the Hammett-type approach.en
dc.language.isoensr
dc.publisherAmsterdam : Elseviersr
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172035/RS//sr
dc.relationinfo:eu-repo/grantAgreement/EC/FP7/261499/EU//sr
dc.rightsrestrictedAccesssr
dc.sourceTetrahedron Letterssr
dc.subjectConformational spacesr
dc.subjectRate constantssr
dc.subjectLinear free-energy relationshipssr
dc.subjectFrontier orbitalssr
dc.titleOn the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethaneen
dc.typearticlesr
dc.rights.licenseARRsr
dcterms.abstractМаринковић, Aлександар Д.; Јуранић, Иван О.; Дракулић, Бранко Ј.;
dc.citation.volume53
dc.citation.issue5
dc.citation.spage553
dc.citation.epage556
dc.identifier.doi10.1016/j.tetlet.2011.11.097
dc.identifier.scopus2-s2.0-84962433241
dc.identifier.wos000300029000021
dc.type.versionpublishedVersionsr


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