Transition metal complexes mediate β-boration of α,β-unsaturated carbonyl compounds highlighting the advantages of using inexpensive catalytic systems, (Cu, Ni), both in the catalytic activity and selectivity. The new C_β–B bond can be accomplished in a stereoselective manner by modifying the metal complex with chiral ligands. Alternative mechanistic studies support the enantioselectivity observed, and large-scale applications of this reaction are currently being developed.