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The first organocatalytic enantioselective direct α-Alkynylation of β-Ketocarbonyls via oxidative decarboxylation coupling is described.In the current reaction,BI-OH serves as an oxidant,the cross coupling between propiolic acids and β-ketocarbonyls undergoes smoothly in the presence of primary amine and Ru(bpy)3Cl2 under the irradiation of blue LEDs.