AgSbF 6 -Catalyzed anti-Markovnikov addition of pinacolborane (HBpin) to terminal alkynes to produce the E-vinylboronates is reported. This efficient methodology is scalable, compatible with sterically and electronically diverse alkynes, and works at room temperature under solvent-free condition. The utility of this method is demonstrated in the facile synthesis of the clinically important (E)-2,4,3′,5′-tetramethoxystilbene. © The Royal Society of Chemistry.