Metal-free selectivity: The first metal-free one-pot three-component highly chemo- and regioselective catalytic synthesis of homoallylboranes using simple N-heterocyclic carbenes (NHC) and amines is presented. The catalytic reaction between B 2(pin) 2, α,β-unsaturated aldehydes and 2-(triphenylphosphoranylidene)acetate esters proceeds through a catalytic metal-free β-boration/Wittig cascade sequence (see scheme). © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.