Photochemical Oxidation of Thioketones by Singlet Molecular Oxygen Revisited: Insights into Photoproducts, Kinetics, and Reaction Mechanism

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dc.contributor.authorSánchez Arroyo, Antonio José
dc.contributor.authorPardo Botero, Zulay D.
dc.contributor.authorMoreno Jiménez, Florencio
dc.contributor.authorHerrera Fernández, Antonio
dc.contributor.authorMartín, Nazario
dc.contributor.authorGarcía Fresnadillo, David
dc.date.accessioned2023-06-18T06:07:08Z
dc.date.available2023-06-18T06:07:08Z
dc.date.issued2015-09-30
dc.descriptionReceived: July 23, 2015; Published: September 30, 2015
dc.description.abstractPhotosensitized oxidation of trimethyl[2.2.1]-bicycloheptane thioketones by 1 O2 can yield more photoproducts than exclusively ketones and sulfines. Moreover, the ketone/sulfine ratio can be reversed when protic conditions and high thioketone concentrations are used, conversely to earlier results reporting ketones as the main photoproducts. A new mechanistic proposal for sulfine formation is suggested following intermolecular oxygen transfer from a peroxythiocarbonyl intermediate to a second thioketone molecule. Reaction quantum yields (10−5−10−2) depend on the reaction conditions and time. Sulfine production reaches a maximum at short irradiation times, whereas decomposition to the corresponding ketone is observed at long reaction times. When the thioketone substrate has a hydrogen atom at the α position a peroxyvinylsulfenic acid intermediate can be formed by proton transfer. Reaction of this intermediate with another thioketone molecule can yield more sulfine and its tautomeric vinylsulfenic acid, which dimerizes in situ to the thiosulfinate. The hydroperoxyl group of the peroxyvinylsulfenic acid can also rearrange to the α position, and by reaction with the starting thioketone, α-hydroxy thioketone and additional sulfine can be formed, while dehydration yields the α-oxo thioketone. In situ [2 + 2] and [4 + 2] self-cycloaddition of the α-oxo thioketone yields significant amounts of the corresponding adducts at prolonged irradiation times.
dc.description.departmentSección Deptal. de Química Orgánica (Óptica y Optometría)
dc.description.departmentDepto. de Química Orgánica
dc.description.facultyFac. de Óptica y Optometría
dc.description.facultyFac. de Ciencias Químicas
dc.description.refereedTRUE
dc.description.sponsorshipMinisterio de Ciencia e Innovación (MICINN)
dc.description.sponsorshipUniversidad Complutense de Madrid
dc.description.statuspub
dc.eprint.idhttps://eprints.ucm.es/id/eprint/69820
dc.identifier.doi10.1021/acs.joc.5b01710
dc.identifier.issn0022-3263 (Print) 1520-6904(Online)
dc.identifier.officialurlhttps://doi-org.bucm.idm.oclc.org/10.1021/acs.joc.5b01710
dc.identifier.urihttps://hdl.handle.net/20.500.14352/23907
dc.journal.titleJournal of organic chemistry
dc.language.isoeng
dc.page.final10584
dc.page.initial10575
dc.publisherACS
dc.relation.projectIDCTQ(2011-24652)
dc.relation.projectIDCT4/14
dc.rights.accessRightsrestricted access
dc.subject.cdu544.526:542.943
dc.subject.cdu542.9
dc.subject.cdu547
dc.subject.keywordKetones
dc.subject.keywordPhotooxidation
dc.subject.keywordChemical reactions
dc.subject.keywordSolvents
dc.subject.keywordIrradiation
dc.subject.ucmQuímica física (Química)
dc.subject.ucmQuímica orgánica (Química)
dc.subject.unesco2306 Química Orgánica
dc.titlePhotochemical Oxidation of Thioketones by Singlet Molecular Oxygen Revisited: Insights into Photoproducts, Kinetics, and Reaction Mechanism
dc.typejournal article
dc.volume.number80
dspace.entity.typePublication
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relation.isAuthorOfPublication09111c59-3829-4b92-a9d2-ee099b545e9e
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relation.isAuthorOfPublication.latestForDiscovery1c9fecf4-c701-46f1-a021-557a6683bbfa
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