Abstract Oxidant-dependent Cu-catalyzed alkynylation and aminomethylation reactions have been achieved under facile and mild conditions. TMEDA coupled with various terminal alkynes via C–H bond cleavage in good yields using atmospheric oxygen as an oxidant. Switching from air to TBHP afforded aminomethylation products of terminal alkynes through C–C bond cleavage of TMEDA. The protocol provided a novel strategy to prepare bi/ ...