We herein disclose a novel palladium-catalyzed 1,2-alkynylarylation of vinyl arenes using haloalkynes and arylboronic acids as coupling partners. This reaction is characterized by broad substrate scope, controllable reaction sequence, and excellent chemo- and regioselectivities. Mechanistic investigations suggest that the reaction is initiated by regioselective insertion of vinyl arenes into the alkynyl-Pd(II) species, and the silver salt is crucial for this transformation, serving as both the Lewis acid and halide scavenger. This protocol provides efficient access to new carbon skeletons, which are embedded in the key biologically active motifs.
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