Abstract The addition of amines to α, β-unsaturated N-acylbenzotriazoles could be catalyzed by samarium triiodide (SmI3) at ambient temperature. α, β-Unsaturated aliphatic N- acylbenzotriazoles afforded bis-addition products (β-amino amides), whereas N- cinnamoylbenzotriazoles gave acylated products (cinnamoylamides) exclusively.