Various iron-salts (and complexes) and especially iron(III) chloride catalyzed the three-component coupling of aldehyde, alkyne, and amine to generate propargylic amines with high efficiency under neat conditions in air. The iron-catalyzed reaction is particularly effective for reactions involving aliphatic aldehydes. The reaction is not sensitive to and occurs smoothly in water and in air. No additional co-catalyst or activator is required. (C) 2009 Elsevier Ltd. All rights reserved.