Hydrogenation of 1,3-enynes in the presence of alpha-keto aldehydes using cationic Rh(I) catalysts enables regio- and stereoselective reductive coupling to the acetylenic terminus of the enyne to afford (E)-2-hydroxy-3,5-dien-1-one products. Reductive condensation of 1-phenyl but-3-en-1-yne 1a with phenyl glyoxal 2a performed under an atmosphere of D(2) provides the product of mono-deuteration, (E)-2-hydroxy-3-deuterio-3,5-dien-1-one deuterio-3a, in 85% yield. Competition experiments involving catalytic hydrogenation of phenyl glyoxal in the presence of equimolar quantities of 1,4-diphenylbutadiene and 1,4-diphenylbut-3-en-1-yne 10a, as well as 1,4-diphenylbut-3-en-1-yne 10a and 1,4-diphenylbutadiyne, are chemoselective for coupling to the more highly unsaturated partner, suggesting a preequilibrium involving precoordination and exchange of the pi-unsaturated pronucleophiles with the catalyst prior to C-C bond formation, as well as a preference for coordination of the most pi-acidic reacting partner, as explained by the Dewar-Chatt-Duncanson model for alkyne coordination.