A zinc enamide generated from the corresponding N-aryl imine undergoes addition to an unactivated olefin, such as ethylene, 1-octene, and isobutylene, to generate an α-alkylated γ- zincioimine intermediate in good to excellent yield. Terminal and gem-disubstituted olefins react with> 99% regioselectivity, allowing the CC bond formation to take place at the more hindered carbon of the double bond. The organozinc intermediate undergoes further CC ...