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Title: | 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 |
Authors: | Magri, David C. Workentin, Mark S. |
Keywords: | Metalloenzymes Energy transfer Fragmentation reactions Peroxides Intermediates (Chemistry) |
Issue Date: | 2008 |
Publisher: | The Royal Society of Chemistry |
Citation: | Magri, 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. |
Abstract: | The 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. |
URI: | https://www.um.edu.mt/library/oar/handle/123456789/69830 |
Appears in Collections: | Scholarly Works - FacSciChe |
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2008 Org Biomol Chem.pdf Restricted Access | 247.29 kB | Adobe PDF | View/Open Request a copy |
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