Rhodium-Catalyzed anti-Markovnikov Addition of Secondary Amines to Arylacetylenes at Room Temperature

An efficient method for synthesis of E-enamines by the anti-Markovnikov addition of secondary amines to terminal alkynes is described. The reaction of a variety of aryl- and heteroarylacetylenes proceeded at room temperature using a combination of a 8-quinolinolato rhodium complex and P(p-MeOC6H4)3 as a catalyst. The products were obtained as enamines by simple bulb-to-bulb distillation.