A Fluorine 1,2-Migration via Aryl Cation/Radical/Radical Anion/Radical Sequence

作者:Pretali Luca; Dondi Daniele; D'Angelantonio Mila; Manet Ilse; Fasani Elisa; Monti Sandra; Bovio Bruna; Albini Angelo*
来源:Organic Letters, 2013, 15(15): 3926-3929.
DOI:10.1021/ol401670p

摘要

Irradiation of a 7-piperazino-8-fluoroquinolone causes formal 1,2-fluorine migration, piperazine loss and reduction, or nucleophile addition in 8. Product study, laser flash photolysis, and computational modeling support F- detachment to yield a triplet 8-quinolyl cation that either inserts intramolecularly or is trapped by Cl-, Br-. However, iodide and pyrrole reduce it to the radical that continues the 'redox tour' (aryl cation -> radical -> radical anion -> radical and then again radical or radical anion) leading to the rearranged products.

  • 出版日期2013-8-2

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