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dc.contributor.authorManley, D.W.
dc.contributor.authorMcBurney, R.T.
dc.contributor.authorWalton, J.C.
dc.contributor.authorMills, A.
dc.contributor.authorO'Rourke, C.
dc.contributor.authorMiller, Philip
dc.date.accessioned2014-03-12T13:01:01Z
dc.date.available2014-03-12T13:01:01Z
dc.date.issued2014-02-07
dc.identifier.citationManley , D W , McBurney , R T , Walton , J C , Mills , A , O'Rourke , C & Miller , P 2014 , ' Titania-promoted carboxylic acid alkylations of alkenes and cascade addition-cyclizations ' Journal of Organic Chemistry , vol. 79 , no. 3 , pp. 1386-1398 . https://doi.org/10.1021/jo4027929en
dc.identifier.issn0022-3263
dc.identifier.otherPURE: 102846444
dc.identifier.otherPURE UUID: d00b442a-4c46-4e23-ad83-3272e6880498
dc.identifier.otherScopus: 84893837502
dc.identifier.otherORCID: /0000-0003-2746-6276/work/56638778
dc.identifier.urihttp://hdl.handle.net/10023/4517
dc.description.abstractPhotochemical reactions employing TiO and carboxylic acids under dry anaerobic conditions led to several types of C-C bond-forming processes with electron-deficient alkenes. The efficiency of alkylation varied appreciably with substituents in the carboxylic acids. The reactions of aryloxyacetic acids with maleimides resulted in a cascade process in which a pyrrolochromene derivative accompanied the alkylated succinimide. The selectivity for one or other of these products could be tuned to some extent by employing the photoredox catalyst under different conditions. Aryloxyacetic acids adapted for intramolecular ring closures by inclusion of 2-alkenyl, 2-aryl, or 2-oximinyl functionality reacted rather poorly. Profiles of reactant consumption and product formation for these systems were obtained by an in situ NMR monitoring technique. An array of different catalyst forms were tested for efficiency and ease of use. The proposed mechanism, involving hole capture at the TiO surface by the carboxylates followed by CO loss, was supported by EPR spectroscopic evidence of the intermediates. Deuterium labeling indicated that the titania likely donates protons from surface hydroxyl groups as well as supplying electrons and holes, thus acting as both a catalyst and a reaction partner.
dc.format.extent13
dc.language.isoeng
dc.relation.ispartofJournal of Organic Chemistryen
dc.rightsCopyright © 2014 American Chemical Society. This is article made open access through ACS AuthorChoice and is distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.en
dc.subjectTiO2en
dc.subjectCarboxylic acidsen
dc.subjectAlkenesen
dc.subjectAryloxyacetic acidsen
dc.subjectPhotoredox catalysten
dc.subjectNMR monitoringen
dc.subjectQD Chemistryen
dc.subject.lccQDen
dc.titleTitania-promoted carboxylic acid alkylations of alkenes and cascade addition-cyclizationsen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1021/jo4027929
dc.description.statusPeer revieweden


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