Titanium‐Catalyzed Intermolecular Hydroaminoalkylation of Alkenes with Tertiary Amines

The first cationic titanium catalyst system for the intermolecular hydroaminoalkylation of alkenes with various tertiary alkylamines is presented. Corresponding reactions which involve the addition of the α‐C−H bond of a tertiary amine across the C−C double bond of an alkene take place at temperatures close to room temperature with excellent regioselectivity to deliver the branched products exclusively. Interestingly, for selected amines, α‐C−H bond activation occurs not only at N‐methyl but also at N‐methylene groups.