A nickel-catalyzed three-component coupling of 1,3-diene, ketone, and organoboron or organosilicon reagents was investigated. While the coupling reaction using PhB(OH)(2) afforded a 1,3-syn-substituted 4-penten-1-ol derivative as a single diastereomer, the reaction in the presence of tetraorganosilicon reagent under similar conditions exclusively produced the corresponding 1,3-anti isomer. In both reactions, a tetrasubstituted carbon center was constructed in a highly diastereoselective manner.