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.
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 beta-scission fragmentation. The rate constant for the heterogeneous ET to the distonic radical-anion is estimated to occur on the order of 2 x 10(7) 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 beta-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.
Magri
David C
DC
Department of Chemistry, The University of Western Ontario, London, Ontario, Canada N6A 5B7.
Workentin
Mark S
MS
D000838:Anions / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D004583:Electrons; D007700:Kinetics; D008954:Models, Biological; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011449:Prostaglandin Endoperoxides / Q000138:chemical synthesis* / Q000737:chemistry; D013816:Thermodynamics
C532514:1,4-diphenyl-2,3-dioxabicyclo(2.2.1)heptane; D000838:Anions; D019086:Bridged Bicyclo Compounds, Heterocyclic; D011449:Prostaglandin Endoperoxides