Abstract The Sonogashira coupling of electron-deficient (hetero) aryl halides 1 and (hetero) aryl or alkenyl 1-propargyl alcohols 2 does not terminate at the stage of the expected internal propargyl alcohols, but rather gives rise to the formation of α, β-unsaturated ketones 3 with a variety of acceptor substituents. This new domino reaction, a coupling– isomerization reaction (CIR), can be rationalized as a sequence of rapid Pd/Cu-catalyzed ...