Remote arylation of amines via C−C bond functionalization has not been reported yet. Herein, we develop the γ-transarylation of amines through the cleavage of unstrained C−C bond enabled by copper catalysis under mild conditions, representing the example of utilization of unstrained C−C bond for metal-catalyzed C−C cross-coupling. Mechanistic investigations reveal that the redox-neutral reaction undergoes an intercepted radical pathway to cleave the C sp 2 −C sp 3 bond, followed by the combination with copper-catalyzed arylation reaction in the presence of aryl boronic acid to construct a new C sp 2 −C sp 3 bond.