Directed Copper-Catalyzed Intermolecular Aminative Difunctionalization of Unactivated Alkenes

A diverse
collection of copper-catalyzed intermolecular aminative
difunctionalizations of unactivated alkenes with N-halodialkylamines as the terminal dialkylamino source is reported.
A bidentate auxiliary tethered on the alkene substrates is crucial,
which can promote the migratory insertion of nonactivated alkenes
into the aminyl radical–metal complex and stabilize the resultant
high-valent copper intermediate to allow for further transformations.
By employing this strategy, the intermolecular aminohalogenation reactions
and a three-component aminoazidation reaction of unactivated alkenes
with dialkylamino source were successively achieved in a remarkable
regio- and stereoselective manner. These reactions were performed
under neutral conditions and maintained excellent functional group
tolerance toward a wide range of N-halodialkylamines
and unactivated alkenes. Further mechanistic studies and DFT calculations
supported a concerted migratory insertion of the C–C double
bond into the aminyl radical–metal complex to form a Cu­(III)
intermediate.