Ligand-controlled diastereodivergent, enantio- and regioselective copper-catalyzed hydroxyalkylboration of 1,3-dienes with ketones.

A copper-catalyzed three-component coupling of 1,3-dienes, bis(pinacolato)diboron, and ketones allows for the chemo-, regio-, diastereo- and enantioselective assembly of densely functionalized tertiary homoallylic alcohols. The relative configuration of the vicinal stereocenters is controlled by the chiral ligand employed. Subsequent transformations illustrate the versatility of these valuable chiral building blocks.