The first rhodium-catalyzed intermolecular hydroamination of alkynes is pre
sented. Terminal alkynes react efficiently with anilines in the presence of
cationic rhodium(I) catalysts under very mild reaction conditions (e.g., b
ase and acid free at room temperature) to yield up to 99% of the correspond
ing imines. An easy one-pot protocol for the synthesis of secondary amines
was developed by combining this alkyne amination reaction with in situ addi
tion of organolithium reagents.