Chemoselectivity of intramolecular hydroaminoalkylation over hydroamination has been achieved with a bis(3-phenyl-2-pyridonate) titanium complex. Primary aminoalkenes are selectively α-alkylated by C-H functionalization adjacent to nitrogen to access five- and six-membered cycloalkylamines with a good substrate-dependent diastereoselectivity of up to 19:1.