The highly chemo-, regio-, and stereoselective synthesis of alkyl-and vinyl boronic esters with good functional group tolerance has been developed using in situ activation of a bench- stable iron (II) pre-catalyst and pinacolborane (16 examples, 45–95% yield, TOF up to 30000 mol h− 1). The first iron-catalysed alkene hydrogermylation is also reported.