Allyl cyanides are found to add across alkynes in the presence of a nickel/P (4-CF3− C6H4) 3 catalyst to give polysubstituted 2, 5-hexadienenitriles with defined stereo-and regiochemistry. Use of AlMe2Cl or AlMe3 as a Lewis acid cocatalyst accelerates the reaction and expands the substrate scope significantly. The cyano group in the allylcyanation products can be transformed to a hydroxymethyl or aminomethyl group to afford highly ...