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On the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane
dc.creator | Drakulić, Branko | |
dc.creator | Marinković, Aleksandar | |
dc.creator | Juranić, Ivan | |
dc.date.accessioned | 2021-03-10T11:56:15Z | |
dc.date.available | 2021-03-10T11:56:15Z | |
dc.date.issued | 2012 | |
dc.identifier.issn | 0040-4039 | |
dc.identifier.uri | http://TechnoRep.tmf.bg.ac.rs/handle/123456789/2222 | |
dc.description.abstract | Rate constants for the esterification of eleven 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane in ethanol at 30 degrees 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.publisher | Pergamon-Elsevier Science Ltd, Oxford | |
dc.relation | info:eu-repo/grantAgreement/EC/FP7/261499/EU// | |
dc.relation | info:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172035/RS// | |
dc.rights | restrictedAccess | |
dc.source | Tetrahedron Letters | |
dc.subject | Conformational space | en |
dc.subject | Rate constants | en |
dc.subject | Linear free-energy relationships | en |
dc.subject | Frontier orbitals | en |
dc.title | On the choice of optimal conformation in linear free-energy relationships. Reactivity of 2-[(carboxymethyl)sulfanyl]-4-oxo-4-arylbutanoic acids with diphenyldiazomethane | en |
dc.type | article | |
dc.rights.license | ARR | |
dc.citation.epage | 556 | |
dc.citation.issue | 5 | |
dc.citation.other | 53(5): 553-556 | |
dc.citation.rank | M22 | |
dc.citation.spage | 553 | |
dc.citation.volume | 53 | |
dc.identifier.doi | 10.1016/j.tetlet.2011.11.097 | |
dc.identifier.scopus | 2-s2.0-84962433241 | |
dc.identifier.wos | 000300029000021 | |
dc.type.version | publishedVersion |