Radical initiation for the perfluoroalkylation reaction of amino(hetero)aromatics has been accomplished employing the complex [(TMEDA)I$I 3 ] and visible light. This methodology circumvents the use of metal(organo)catalysts and biologically-relevant substrates are easily substituted with R F moieties employing a mild and environmentally benign radical strategy starting from readily-available perfluoroalkyl iodides R F I.
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