Version 2 2024-02-08, 13:34Version 2 2024-02-08, 13:34
Version 1 2024-02-06, 21:24Version 1 2024-02-06, 21:24
journal contribution
posted on 2024-02-08, 13:34authored byNicholas
D. Chiappini, Eric P. Geunes, Ethan T. Bodak, Robert R. Knowles
A light-driven method for the generation of aryl radicals
from
triarylbismuth(III) and (V) reagents is described. Aryl radical generation
is proposed to occur through the ligand-assisted mesolytic cleavage
of an organobismuth(IV) intermediate generated from either oxidation
of BiIII or reduction of BiV. This mode of aryl
radical generation is demonstrated to be compatible with a range of
bimolecular radical arylations, including hydroarylation of electron-deficient
olefins and arylation of diboronates, disulfides, sulfonyl cyanides,
phosphites, and isocyanides. The intermediacy of an aryl radical is
supported by radical trapping and radical clock experiments, and BiIV–aryl mesolysis is supported computationally.