Abstract A method for the synthesis of pinacol boronic esters bearing a fluorinated group at the α-carbon atom (R f CH 2 Bpin) from corresponding bromomethyl borane (BrCH 2 Bpin) and fluorinated silanes (R f SiMe 3) is described. The fluoroalkylation reaction involves formation of borate anions followed by intramolecular nucleophilic substitution of bromine.