Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/155849
Share/Export:
logo share SHARE logo core CORE BASE
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE
DC FieldValueLanguage
dc.contributor.authorChiacchio, Maria A.-
dc.contributor.authorLegnani, Laura-
dc.contributor.authorCaramella, Pierluigi-
dc.contributor.authorTejero, Tomás-
dc.contributor.authorMerino, Pedro-
dc.date.accessioned2017-09-29T09:20:58Z-
dc.date.available2017-09-29T09:20:58Z-
dc.date.issued2017-
dc.identifierdoi: 10.1002/ejoc.201700127-
dc.identifiere-issn: 1099-0690-
dc.identifierissn: 1434-193X-
dc.identifier.citationEuropean Journal of Organic Chemistry 2017(14): 1952-1960 (2017)-
dc.identifier.urihttp://hdl.handle.net/10261/155849-
dc.description.abstractThe mechanism of the thionation of alcohols with Lawesson's reagent was explored through quantum chemical DFT methods. Evidence that carbocations are involved was found. The mechanism is completely different to that established recently for the thionation of carbonyls. The presence of a phenyl ring at the alcoholic carbon atom exerts a pivotal role in the stability of the carbocation and enables a S–π interaction, which is crucial for favoring thionation instead of undesired elimination. The influence of the solvent was also studied, and elimination is preferred in toluene, whereas substitution leading to thionation is favored in acetonitrile. A clear correlation between solvent polarity and elimination was observed. The study is in complete agreement with the different behavior observed experimentally for primary, secondary, and tertiary alcohols (bearing a phenyl ring or not), and the best conditions for minimizing undesired elimination can be predicted.-
dc.description.sponsorshipThis work was supported by the Spanish Ministerio de Economía y Competitividad (MINECO) (project number CTQ2016-76155-R), the Fondos Europeos para el Desarrollo Regional (FEDER), and the Gobierno de Aragón (Zaragoza, Spain, Bioorganic Chemistry Group, E-10). M.-A. C. thanks the University of Catania for partial financial support. L. L. thanks the University of Pavia for partial financial support.-
dc.relationMINECO/ICTI2013-2016/CTQ2016-76155-R-
dc.rightsclosedAccess-
dc.subjectThiols-
dc.subjectAlcohols-
dc.subjectDensity functional calculations-
dc.subjectCarbocations-
dc.subjectReaction mechanisms-
dc.titlePivotal neighboring-group participation in substitution versus elimination reactions – computational evidence for ion pairs in the thionation of alcohols with Lawesson's reagent-
dc.typeartículo-
dc.identifier.doi10.1002/ejoc.201700127-
dc.date.updated2017-09-29T09:20:58Z-
dc.description.versionPeer Reviewed-
dc.language.rfc3066eng-
dc.contributor.funderGobierno de Aragón-
dc.contributor.funderEuropean Commission-
dc.contributor.funderMinisterio de Economía y Competitividad (España)-
dc.contributor.funderUniversità degli Studi di Catania-
dc.contributor.funderUniversità degli studi di Pavia-
dc.relation.csic-
dc.identifier.funderhttp://dx.doi.org/10.13039/501100003329es_ES
dc.identifier.funderhttp://dx.doi.org/10.13039/501100000780es_ES
dc.identifier.funderhttp://dx.doi.org/10.13039/501100004769es_ES
dc.identifier.funderhttp://dx.doi.org/10.13039/501100010067es_ES
item.fulltextNo Fulltext-
item.openairetypeartículo-
item.cerifentitytypePublications-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.grantfulltextnone-
Appears in Collections:(ISQCH) Artículos
Files in This Item:
File Description SizeFormat
accesoRestringido.pdf15,38 kBAdobe PDFThumbnail
View/Open
Show simple item record

Google ScholarTM

Check

Altmetric

Dimensions


WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.