A convenient three‐component coupling reaction for the construction of conjugated enynes using rhodium catalysis is reported. Dimerization of a monosubstituted alkyne followed by trapping of the vinyl metal intermediate with an electron‐deficient alkene, such as methyl vinyl ketone, provided moderate to good yields of these enynes. The use of the hindered electron‐rich tris(ortho‐tolyl)phosphine as a ligand for the rhodium catalyst provided the best conversions to these complex products.
