We report ar ange of highly regioselective openings of [1.1.1]propellane with various allylic zinc halides,aswell as zinc enolates of ketones,e sters and nitriles.T he resulting zincated bicyclopentanes (BCPs) were trapped with arange of electrophiles including acyl chlorides,sulfonothioates,hydroxylamino benzoates,t osyl cyanide as well as aryl and allyl halides,generating highly functionalized BCP-derivatives.The unusually high regioselectivity of these reactions has been rationalized using DFT calculations.Abioisostere of the synthetic opioid pethidine was prepared in 95 %y ield in one step using this method.