We report a novel approach for the sequential perfluoroalkylation and defluoroamination of indoles. This transformation proceeds under mild conditions and exhibits good functional group tolerance, affording a series of valuable α-perfluoroalkylamino indole derivatives in yields up to 80%. Mechanistic investigations support a cascade process involving sulfinate-derived perfluoroalkyl radicals, followed by hexamethyldisilazane (HMDS)-mediated C-F bond cleavage and C-N bond formation. This work provides a versatile and practical strategy for the defluorinative functionalization of inert perfluoroalkyl groups, opening new avenues for synthesizing structurally diverse heteroarenes containing nitrogen-substituted perfluoroalkyl motifs.
Gao et al. (Mon,) studied this question.