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- W2951750255 abstract "Under the 9,10-dicyanoanthracene (DCA)-sensitized photoinduced electron-transfer (PET) conditions, 2,5-diaryl-3,3,4,4-tetradeuterio-1,5-hexadiene (d4-1) undergoes a degenerate Cope rearrangement to give a photostationary mixture of d4-1 and its 1,1,6,6-tetradeuterio analogue d4-1‘ in 52:48. This reaction involves 1,4-diaryl-2,2,3,3-tetradeuteriocyclohexane-1,4-diyl cation radical (d4-2•+), which can be captured by molecular oxygen as 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octane (3). In contrast, nonphotoinduced electron-transfer (non-PET) reaction of d4-1 with cerium(IV) ammonium nitrate similarly forms d4-2•+, but the degenerate Cope does not take place. This observed striking contrast between PET and non-PET was ascribed to the formation of 1,4-diaryl-2,2,3,3-tetradeuteriocyclohexane-1,4-diyl (d4-2) in the PET process by back-electron transfer from DCA•- to d4-2•+. The results of similar PET and non-PET reactions of 1,4-diphenyl-2,3-diazabicyclo[2.2.2]oct-2-ene (4c) and its 5,5,6,6-tetradeuterio analogue (d4-4c) support this conclusion. Photoacoustic calorimetry of the PET reaction of 2,5-diphenyl-1,5-hexadiene (1c) suggests that 1,4-diphenylcyclohexane-1,4-diyl (2c) lies ca. 18.8 kcal/mol higher in energy than 1c and ca. 25.6 kcal/mol below the ion-radical pair [2c•+/DCA•-]. Deazetation of d4-4c demonstrates that d4-2c undergoes cleavage to d4-1c and d4-1c‘ with bond-breaking kinetic isotope effects, k(d4-2c)H4 / k(d4-2c)D4 = 1.11, completing a cation-radical cyclization−diradical cleavage mechanism." @default.
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- W2951750255 date "1998-01-01" @default.
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- W2951750255 title "Photoinduced Electron-Transfer Degenerate Cope Rearrangement of 2,5-Diaryl-1,5-hexadienes: A Cation-Radical Cyclization−Diradical Cleavage Mechanism" @default.
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- W2951750255 doi "https://doi.org/10.1021/ja971910s" @default.
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