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dc.creatorAleksić, Jovana
dc.creatorStojanović, Milovan
dc.creatorBaranac-Stojanović, Marija
dc.date.accessioned2019-01-30T17:47:35Z
dc.date.available2019-01-30T17:47:35Z
dc.date.issued2015
dc.identifier.issn0022-3263
dc.identifier.urihttp://cer.ihtm.bg.ac.rs/handle/123456789/1814
dc.description.abstractThe well-known gauche preference in FCCX systems, where X is an electronegative element from Period 2, is widely exploited in synthetic, medicinal, and material chemistry. It is rationalized on the basis of sigma(C-H)->sigma*(C-F) hyperconjugation and electrostatic interactions. The recent report (Thiehoff, C.; et al. Chem. Sci. 2015, 6, 3565) showed that the fluorine gauche effect can extend to Period 3 elements, such as sulfur. The aim of the present work is to disclose factors governing conformational behavior of FCCS containing systems. We examine conformational preferences in seven classes of compounds by ab initio and DFT calculations and rationalize the results by quantitatively decomposing the anti/gauche isomerization energy into contributions from electrostatic, orbital, dispersion, and Pauli interactions, and energy spent on structural changes. The results show that the fluorine/sulfur gauche effect is primarily electrostatic (63-75%), while all orbital interactions contribute 22-41% to stabilizing interactions. Stereoelectronic effects, involved in orbital interactions, also play a role in gauche conformer stabilization.en
dc.publisherAmerican Chemical Society (ACS)
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172020/RS//
dc.rightsrestrictedAccess
dc.sourceJournal of Organic Chemistry
dc.titleOrigin of Fluorine/Sulfur Gauche Effect of beta-Fluorinated Thiol, Sulfoxide, Sulfone, and Thionium Ionen
dc.typearticle
dc.rights.licenseARR
dcterms.abstractСтојановић, Милован; Баранац-Стојановиц, Марија; Aлексић, Јована;
dc.citation.volume80
dc.citation.issue20
dc.citation.spage10197
dc.citation.epage10207
dc.citation.other80(20): 10197-10207
dc.citation.rankM21
dc.identifier.pmid26378891
dc.identifier.doi10.1021/acs.joc.5b01779
dc.identifier.rcubConv_3429
dc.identifier.scopus2-s2.0-84944930016
dc.identifier.wos000363224600040
dc.type.versionpublishedVersion


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