Two C(sp3)–F Bond Activation in a CF3 Group: ipso-Defluorinative Amination Triggered 1,3-Diamination of (Trifluoromethyl)alkenes with Indoles, Carbazoles, Pyrroles, and Sulfonamides

A novel strategy enabled cleavage of two C(sp3)-F bonds in a CF3 group is reported. Triggered by ipso-defluorinative amination, this 1,3-diamination of (trifluoromethyl)alkenes with indoles, carbazoles, pyrroles, and sulfonamides gave acyclic 1,3-diamine products bearing a monofluoroalkene moiety in high yields with good to excellent Z/E selectivities. Preliminary mechanistic studies enable the isolation of the reaction intermediate and indicate that a unique sequential ipso-/γ-selective defluorinative amination pathway is involved in this transformation.