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A computational study on the electronic nature of radical anions generated from various N1-substituted 5-fluorouracil derivatives and their preferred fragmentation pathway has been recently reported (Borosky, G. L.; Nishimoto, S.; Pierini, A B. J. Mol. Struct. THEOCHEM 2000, 499, 151-160). This indicated that while the most stable radical anion is of π-type for general N1-substituents, increase in the electron affinity of the N1-substituents can enhance the spin density at the C(1′)-N(1) bond favoring the formation of a C(1′)-N(1) isomer of radical anion intermediates. According to this result, it seems plausible that the electron-adduct of 5-fluorouracil derivatives 3-11 bearing 2′-oxoalkyl substituents at N(1) could have a (π* + σ*) SOMO energy level closer to or even lower than the σ* level.
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