Abstract: Organoboron reagents are well known formetal-mediated crosscouplings and as radical precursors. They are alsoremarkable nucleophiles that readily react directly (i.e., without metalcatalysis) with carbocationic intermediates for a variety of chemo-, regio-,diastereo-, and enantioselective reactions. Recent advances in this fieldwill be presented with an emphasis on mechanism, catalysis, and diversity oftransformations.