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Organocatalyzed oxidation of benzyl alcohols by a tetrazole-amino-saccharin: A combined experimental and theoretical (DFT) study

2017-12Journal article Restricted access
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dc.contributor.authorFrija, Luis M. T.
dc.contributor.authorKuznetsov, Maxim L.
dc.contributor.authorRocha, Bruno G. M.
dc.contributor.authorCabral, LĂ­lia
dc.contributor.authorCristiano, Maria Lurdes Santos
dc.contributor.authorKopylovich, Maximilian N.
dc.contributor.authorPombeiro, Armando J. L.
dc.date.accessioned2019-11-20T15:07:10Z
dc.date.available2019-11-20T15:07:10Z
dc.date.issued2017-12
dc.description.abstractA new catalytic system for the anaerobic oxidation of benzyl alcohols using a tetrazole-amino-saccharin organocatalyst has been established. In a solvent-free and microwave assisted process comprising aqueous tert-butyl hydroperoxide (TBHP) as oxidant, a variety of benzyl alcohols has been efficiently converted to aldehydes under mild conditions. Most reactions are complete within 30 min and the catalyst exhibits varied functional group compatibility. A catalytic cycle for the oxidation of the alcohols promoted by the tetrazole-amino-saccharin derivative is outlined involving radical species. DFT calculations performed for the oxidation of benzyl alcohol with and without organocatalyst show that the rate limiting step of the whole reaction is the cleavage of the O-O bond in TBHP with the subsequent hydrogen abstraction from the alcohol. The tetrazole-amino-saccharin organocatalyst assists the H-abstraction from benzyl alcohol by the bound HO center dot radical. The simplicity, selectivity and softness of reaction conditions of the studied organocatalytic protocol suggest a great potential for extensive use in synthetic chemistry. (C) 2017 Elsevier B.V. All rights reserved.
dc.description.sponsorshipFoundation for Science and Technology (FCT), Portugal [IF/01270/2013/CP1163/CT0007]
dc.description.sponsorshipFCT [SFRH/BPD/99851/2014, SFRH/BD/52370/2013, PD/00248/2012]
dc.identifier.doi10.1016/j.mcat.2017.09.003
dc.identifier.issn2468-8231
dc.identifier.urihttp://hdl.handle.net/10400.1/12916
dc.language.isoeng
dc.peerreviewedyes
dc.publisherElsevier Science Bv
dc.subjectShock-tube
dc.subjectPeroxidative oxidation
dc.subjectCopper(Ii) complexes
dc.subjectEffective catalysts
dc.subjectSolvent
dc.subjectOh
dc.subjectChemistry
dc.subjectWater
dc.subjectHydroxylation
dc.subjectDerivatives
dc.titleOrganocatalyzed oxidation of benzyl alcohols by a tetrazole-amino-saccharin: A combined experimental and theoretical (DFT) study
dc.typejournal article
dspace.entity.typePublication
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/5876/UID%2FQUI%2F00100%2F2013/PT
oaire.citation.endPage65
oaire.citation.startPage57
oaire.citation.titleMolecular Catalysis
oaire.citation.volume442
oaire.fundingStream5876
person.familyNameCabral
person.familyNameCristiano
person.givenNameLĂ­lia
person.givenNameMaria de Lurdes
person.identifier.ciencia-id3510-24A8-36B6
person.identifier.ciencia-idE411-6006-5A01
person.identifier.orcid0000-0001-9362-8128
person.identifier.orcid0000-0002-9447-2855
person.identifier.ridM-4279-2013
person.identifier.ridG-2345-2012
person.identifier.scopus-author-id9238724800
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a CiĂȘncia e a Tecnologia
rcaap.rightsrestrictedAccess
rcaap.typearticle
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relation.isAuthorOfPublicationb16751a6-748e-44b0-9c59-058cbd5b2cc3
relation.isAuthorOfPublication.latestForDiscoveryb16751a6-748e-44b0-9c59-058cbd5b2cc3
relation.isProjectOfPublication9afed05e-58cb-478e-acc7-625439f9c745
relation.isProjectOfPublication.latestForDiscovery9afed05e-58cb-478e-acc7-625439f9c745

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