Alkene Diamination Using Electron-Rich Amines: Hypervalent Iodine-Promoted Inter-/Intramolecular C-N Bond Formation

A combined inter-/intramolecular oxidative diamination of terminal alkenes is described that uses a hypervalent iodine oxidant and a nucleophilic amine to produce 3-aminoindolines at room temperature. This operationally straightforward and metal-free protocol is compatible with a broad range of functional groups. A mechanism involving the conversion of the amine to an electrophilic nitrogen source is advanced and used to identify a protocol effective with substoichiometric amounts of iodide and commercially available phenyl iodobenzene diacetate (PIDA) as the stoichiometric oxidant.