The development of a ligand-assisted Pd-catalyzed C–H alkenylation of aliphatic amines is reported. Our studies indicated that an amino-acid-derived ligand renders the C–H bond activation step reversible and promotes the traditionally difficult alkenylation process. The C(sp$\mathrm{<mrow\; data-mjx-texclass="ORD">3</mrow>}$)–H alkenylation proceeds through a 5-membered-ring cyclopalladation pathway that allows access to complex aliphatic heterocycles that could be useful to practioners of synthetic and medicinal chemistry.