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dc.contributor.authorMagri, David C.-
dc.contributor.authorWorkentin, Mark S.-
dc.date.accessioned2021-02-23T07:50:09Z-
dc.date.available2021-02-23T07:50:09Z-
dc.date.issued2008-
dc.identifier.citationMagri, D. C., & Workentin, M. S. (2008). A radical-anion chain mechanism following dissociative electron transfer reduction of the model prostaglandin endoperoxide, 1, 4-diphenyl-2, 3-dioxabicyclo [2.2. 1] heptane. Organic & Biomolecular Chemistry, 6(18), 3354-3361.en_GB
dc.identifier.urihttps://www.um.edu.mt/library/oar/handle/123456789/69830-
dc.description.abstractThe model prostaglandin endoperoxide, 1,4-diphenyl-2,3-dioxabicyclo[2.2.1]heptane (3), was investigated in N,N-dimethylformamide at a glassy carbon electrode using various electrochemical techniques. Reduction of 3 occurs by a concerted dissociative electron transfer (ET) mechanism. Electrolysis at −1.6 V yields 1,3-diphenyl-cyclopentane-cis-1,3-diol in 97% by a two-electron mechanism; however, in competition with the second ET from the electrode, the resulting distonic radical-anion intermediate undergoes a b-scission fragmentation. The rate constant for the heterogeneous ET to the distonic radical-anion is estimated to occur on the order of 2 × 107 s−1 . In contrast, electrolyses conducted at potentials more negative than −2.1 V yield a mixture of primary and secondary electrolysis products including 1,3-diphenyl-cyclopentane-cis-1,3-diol, 1,3-diphenyl-1,3-propanedione, trans-chalcone and 1,3-diphenyl-1,3-hydroxypropane by a mechanism involving less than one electron equivalent. These observations are rationalized by a catalytic radical-anion chain mechanism, which is dependent on the electrode potential and the concentration of weak non-nucleophilic acid. A thermochemical cycle for calculating the driving force for b-scission fragmentation from oxygen-centred biradicals and analogous distonic radical-anions is presented and the results of the calculations provide insight into the reactivity of prostaglandin endoperoxides.en_GB
dc.language.isoenen_GB
dc.publisherThe Royal Society of Chemistryen_GB
dc.rightsinfo:eu-repo/semantics/restrictedAccessen_GB
dc.subjectMetalloenzymesen_GB
dc.subjectEnergy transferen_GB
dc.subjectFragmentation reactionsen_GB
dc.subjectPeroxidesen_GB
dc.subjectIntermediates (Chemistry)en_GB
dc.titleA radical-anion chain mechanism following dissociative electron transfer reduction of the model prostaglandin endoperoxide, 1,4-diphenyl-2,3- dioxabicyclo[2.2.1]heptaneen_GB
dc.typearticleen_GB
dc.rights.holderThe copyright of this work belongs to the author(s)/publisher. The rights of this work are as defined by the appropriate Copyright Legislation or as modified by any successive legislation. Users may access this work and can make use of the information contained in accordance with the Copyright Legislation provided that the author must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the prior permission of the copyright holder.en_GB
dc.description.reviewedpeer-revieweden_GB
dc.identifier.doi10.1039/b809356c-
dc.publication.titleOrganic & Biomolecular Chemistryen_GB
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