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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Organobismuth Compounds as Aryl Radical Precursors via Light-Driven Single-Electron Transfer
Nicholas D Chiappini1, Eric P Geunes1, Ethan T Bodak1
1Department of Chemistry, Princeton University, Princeton NJ, 08544.
None:
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 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.
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