Enaminones are synthesized by the rhodium(II)-catalyzed denitrogenative rearrangement reaction of 1-(N-sulfonyl-1,2,3-triazol-4-yl)alkanols, which are readily prepared from propargylic alcohols and N-sulfonyl azides. Intramolecular 1,2-hydride (or -alkyl) migration occurs with an intermediary alpha-imino rhodium-(II) carbenoid species generated through denitrogenation of the 1,2,3-triazol-4-yl moiety. The resulting enaminones is converted into various heterocycles with replacement of the N-sulfonyl group.