Copper-Mediated Perfluoroalkylation of Heteroaryl Bromides with (phen)CuR(F)

[Image: see text] The attachment of perfluoroalkyl groups onto organic compounds has been a major synthetic goal over the past several decades. Previously, our group reported phenanthroline-ligated perfluoroalkyl copper reagents, (phen)CuR(F), which react with aryl iodides and aryl boronates to form the corresponding benzotrifluorides. Herein the perfluoroalkylation of a series of heteroaryl bromides with (phen)CuCF(3) and (phen)CuCF(2)CF(3) is reported. The mild reaction conditions allow the process to tolerate many common functional groups. Perfluoroethylation with (phen)CuCF(2)CF(3) occurs in somewhat higher yields than trifluoromethylation with (phen)CuCF(3), creating a method to generate fluoroalkyl heteroarenes that are less accessible from trifluoroacetic acid derivatives.