An enamine-controlled hydroacylation of alkynes using a rhodium(I)/dppe catalyst system is described. The reaction is highly selective, forming the linear enaminone products as single regioisomers in all examples. In situ hydrolysis of the enamine functionality generated α-substituted 1,3-diketone products, and Lewis-acid mediated intramolecular conjugate addition of the hydroacylation products gave substituted hexahydroquinolones
